Coordination Chemistry reviews

Coordination Chemistry reviews

Coordination Chemistry Reviews, 89 (1988) l-255 EisevierSciencePublisheraB.V.,Amsterdam-PPrintedinTheNetherlands 1. PALLADIUM P.A. CHALOIWR AND ...

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Coordination Chemistry Reviews, 89 (1988) l-255 EisevierSciencePublisheraB.V.,Amsterdam-PPrintedinTheNetherlands

1.

PALLADIUM

P.A.

CHALOIWR

AND

PLATINUM

CONTERTS

.............................. Introduction ................... 1.1 Palladium(V1) and Platinua(VI) .................... 1.2 Palladium(V) and Platinum(V) ................... 1.3 Palladium(IV) and Platinum(IV) 1.3.1 Complexes with Group 17 donor iigands ............ 1.3.2 Complexes with Group 16 donor ligands ............ ..................... 1.3.3 Cancer chemotherapy ............ 1.3.4 Complexes with Group 15 donor ligands ............ 1.3.5 Complexes with Group 14 donor ligands 1.4 Palladium and Platinum complexes with mixed (IV/II) oxidation states .................. 1.5 Palladium(II1) and Platinum(II1) ................... 1.6 Palladium(II) and Platinur(I1) ............ 1.6.1 Complexes with Group 17 donor ligands ............ 1.6.2 Complexes with Group 16 donor ligands and nucleic acids .... 1.6.3 Complexes with amino acids, peptides ............ 1.6.4 Complexes with Group 15 donor liganda 1.6.5 Complexes with Group 14 donor ligands ............ 1.6.6 Hydride complexes ...................... .................... 1.7 Palladium(I) and Platinum(I) .................... 1.8 Palladium(O) and Platinum(O) ............ 1.8.1 Complexes with Group I6 donor ligands 1.8.2 Complexes with Group 15 donor ligands ............ 1.8.3 Complexes with Group 14 donor ligands ............ .................. 1.9 Palladium and Platinum clusters 1.9.1 Trimeric clusters ...................... ..................... 1.9.2 Tetrameric clusters 1.9.3 Higher nuclearity clusters .................. 1.9.4 Heteronuclear clusters .................... ........... 1.10 Catalysis by Palladium and Platinum complexes 1.10.1 Hydrogenation and hydrogenolysis .............. 1.10.2 Carbon monoxide reactions .................. .......................... 1.10.3 Oxidation 1.10.4 Other additions to alkenes and alkynes ........... 1.10.5 Isomerisation ........................ 1.10.6 Allylic substitution .................... 1.10.7 Coupling of carbanions with halides ............. telomerisation and polymerisation ..... 1.10.8 Oligonerisation, 1.10.9 Other coupling reactions .................. 1.10.10 Other reactions catalysed by palladium and platinum complexes ......... 1.11 Non-stoicheiometric, binary and ternary compounds 1.11.1 Compounds with Group 17 elements .............. 1.11.2 Compounds with Group 16 elements .............. 1.11.3 Compounds with Group 15 elements .............. 1.11.4 Compounds with silicon ................... 1.11.5 Other compounds ....................... References ...............................

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2

INTRODUCTION

This

review

Volume

99,

issues

of

although are

covers

mainly

25

26

issues the

most

also

and

major of

and

English

the papers

included,

the

papers

Volumes

language covered

100

and

in

101.

inorganic

were

with

together

recorded

as

well

chemistry

published

Abstracts

as

slow

the

to

from

reach

1984

Thus,

journals.

in 1984. many

work

earlier

Chemical

1983

Chemical

Abstracts. Once

again

expansion

the number

being

bloaedical

General

reviews

of paramagnetic

published

group metals

1.1 PALLADIUM(V1)

their

boiling

from

The

or

to

Hz[PtCls].

have

included

an account

[l], a discussion

of the industrial

of the species

arise

between

points

of all

the

of complexes

toxicology

for polymerlsation from

the

the latter presumably

2[NF,] + FZ + 2[PtF6]

been

of the

it has

been

used

to

and fusion and as an oxidatlve (1)) and CIFS

electron

transfer

on alumina

claimed

of 2-propene-l-01,

being the catalyst

-

[PtFsJ, has been

(reaction

formed

inability

authors'

been

involved

have

[S]. Whilst

has

of fluorine

proposed

catalysts

including

of vapourfsation

[PtFs]

[4].

mechanism metal

[MPG].

heats

in the presence

[Pt(PF3)4]

used as a catalyst seems

NF,

platinum

[PtFs]

and

cancer

on

[S].

and aeltlng

(2)). of

silicides

section

AND PLATINlJW(V1)

towards

(reaction Deposits

The

of greatest

expanded.

and Wallbridge

in terms of correlation

fluorinator

the areas

of the metal

complexes.

[Z]. and a review

The ease of preparation studied

increased,

the chemistry

this year

by Taylor

llgands

has

platinum

of

has been considerably

group metals

platinum

reactions,

applications

chemotherapy

platinum

catalytic

of references

that

or

[PtCl=]

this unlikely

used

was

remark

[PtCI, ]

distinguish actually

[53_ quartz

and

(71. (1)

2[NF,][PtFa]

HP, 25 lC 2[ClF53

+ 2[PtFs]

The

electronic

affinity platinum

of

the

formed

chromothernographic evidenced [PtOB(OH)]

by mass

CClF4lEPtFel + CC1FslCPtFsl

c structure neutral in

[PdO, ]-

of

species

air column.

at

spectrometric

calculated

estimated

[a].

Compounds

were

isolated

was

data, [S].

adsorbed

and species

at

the

and

725 f 25 'C

Ptoa

were also postulated

was

(2)

high

of the type

of on

electron

radioactive a

quartz

temperature, [Pt&(OH)z]

as and

3 1.2

PALLADIUM(V)

Two

AND

papers

have

[RIP,]- (M = Pd within

1.3

or

conditions determined

[133.

The

concentrations

reviewed

1.3-l

Gaseous admitting solid

and

by

their

and

in

in

the

b.

ligand of of

media in

the

optimum

The

alkaline

of

the

quantities

currents

presence

been

catalysis

chlorophyll

polarographic

have of

Trace

reactions

catalytic

[PtF&]

were

determining

platinum(I1)

has

been

data

the

Pt[SG41Z to

of

then

population

had

resistant

[Pt(NH,),Cl,]

glutathione

to

2KP

and

for

The

and

inhibition acid.

by

addition

of

fluorine

and

platinum

metal

with

were

accounted

enthalpy

of

(-495

K+[PtFs]

reaction

for

(3)

kJ mol-I),

(-2055

rating to

five

the

yielded

I

K,CPdP,

kJ nol-*)

were

H2[PtCls]

toxic

effects cells

[lS].

stable

for

in

was vitro

H*[PtCla] the

at

was

of

K2[PtCle] continuous

The

least

inhibition was

have

two

cell

fifty-five some

specific,

conferred

inhibition

PdCl?

by

respectively.

resistance

their

and

ovary

months

complexes

by

of

hamster

which

Since

on

(3)

each

for

or

by

Pz

and

platinum

cell,

conditions

platinum

PdF+

and

Chinese

four

examined

ascorbic

the

hygenic

Whilst

ATPase.

of

of

+

phenotypes

other

were

of

equilibrium

effusion

resistances in

under

from

kJ mol-I)

+

Cellular

doublings.

cross-resistance

microsonal

(-681

compounds

reaction

fluorine

induced

were the

platinum

Analysis

toxicology

[17].

generated

formation

MFZ

on

a

the

of

[15].

-

reviewed

exposure

for

[PtFI]

ligands

were

into

desorption grounds

donor

17

fluorine

sol-*),

Data

and

of

analysis

determined a

platinur(IV)

enthalpies kJ

2Kz u-61

lines

been

An

[=I-

series

have

chemiluminescence

Croup

Kinetic

flash

standard

and

with

gaseous

thermodynamic

been

[lO.ll].

complexes

contributions.

chlorophyll

use of

[PtPP]

MM,. on

(-2040

functions

of

X, method

[14].

complexes

data

structures

variational

platinum(IV)

magnetochemical

of

the

in

ligand

platinum(I1)

for

electronic

discrete

Hartree-Pock

shifts and

oxidation

periodate

the

the

PLATINUM(IV)

a

and

using

of numerical

metal

gave

of

calculations others)

chemical

into

platinum(IV)

trace

AND

ion

parameters

among

basis

PALLADIUW(IV)

paraaetrised

reported

Pt

an extended

Metal

PLATINUM(V)

reduced of

IlS]. of

Hz[PtCls] human

by ATPase

renal

cysteine. may

be

associated toxicity

with

tubular

measured

K absorption

and explained

ascribed

lowest

spectra

of ground

by inelastic The

ion radical

solution

tunnel

librational

been

limited

to

nmr

splitting

for

measurements

the observation

ions

attempt

was

through

considered field

the

Kp[PtCls]

[PdCla]*-

diffraction

distribution

and

the

[Pt(CN).Br2]*-

[22]. The pressure

and the energy

observation

of

applications

molar

of transition

the

to

was measured

complexes l==Pt

w41-

force

representation and

[PtCla]*used

The

nucleus

linewidth

with nmr

and Nap[Pt(OH)p]

unique

rosPd

of this technique

was

will be

spectroscopic base have

[ZS].

fields

of

method

some

of

(XY,}

Strey.

[ZS]. A new programme

for

in

solution

in aqueous

due to mixed species

the

was

consideration

direction 5d

at

0.5 A

or

and electronic

Extraction quantitative from these

of at

Platinum

was

[28].

were

diffraction in

a peak This

orbital

or ephedrine)

of

type

Species

for ligand

Re4+

ions

by reaction

reduction

is

thought

The

salts

prepared

in

by

as of

the

with

with

be

the

for

by

proved

lHLlt CPtCLl by

[29].

at pH 4-10

[PtClb]*-

to

in the

[RSNH]2[PtCls]

characterised [SO].

was shown N1923 and platinum could

of thallium(II1))

eA_'

The complexes

were

collector

density

and characterised

chemistry

with Na[BH,]

served

of 0.5(2)

and X-ray phase analysis

PdCIZ

and

the electron

techniques.

forensic

[Sl]. Palladium

by reduction dioxide

determined

by electrochemical

showed

platinum.

ttg

spectroscopy

Hz[PtC1a]

solutions

Manganese

has revealed

2.3-benzo-4-azafluorene)

low acidity

K[Mn04].

a

and X-ray analysis

amine

(L = I-azafluorene infra-red

from in

cocaine

spectroscopy for

X-X synthesis

electrons

(R3N = amphetamine, infra-red

study of K2[PtCls]

in the anion.

non-bonding

useful

fix

calculations

[PtClsJ2-

for

[27].

An X-ray



to

new transitions

data

structure

to the

reflectance

[NHI]+. in [NH,]ZIPdClb],

of Na.[PtCle]

parametric

included

theory

1

of signals

made

and several

palladium(W)

than

on a mixture

diffuse

H,[PdCle]/HCl/Cl,/H~NO~].

symmetric

greater

The

1s orbital

[23].

spectroscopic

reported

very

concentrations

[ZO].

salts with

1200 Hz and it is likely that chemical

An

of platinum

line at the threshold

spectroscopic

state of

scattering

direct

has

egu*

of their electronic

state

neutron

first

white

from a chlorine

emission

led to a determination

the first excited

intense

orbital,

X-ray

dibenzotetrathiofulvalene

allowed

to studies

(M = K or [NH,]) have been

at 90 K has been determined

c211-

dependence

The

transition

antibonding

of K2[PtCls]

localised

of &[PtCl.]

by MO‘theory.

to an electronic

unoccupied

spectrum

have

such data are relevant

[Is].

The chlorine

was

damage,

to be

be

near

recovered

in the presence the

metals

thallium(I)

deposition

of

1321.

(produced

of Tlz [PtCg]

5

on the electrode

for gravimetric

to mathematical

analysis

Impregnation spectroscopy H[ReO,] and

In

on r-alumina

the

the

alumina

of

dioxide

on

to

it.

resulting

c373. The

effect

platinum

and

The

the

or

the

catalytic

temperature,

and

chemisorption

of

general

the

solution.

metal

ions

it

with

form a Pt-TiO* from

present,

to be

greater

containing catalyst

a buffer whilst

than

bath

free

sintered coating

platinum

containing

at

400-600

and

the

other

semiconductors band electrons

sulphide visible low

PtF4

form

or

an

substrate

light

Thus

143).

[44]. Platinum were

colloidal

produced

by

in two

preparation

of

the metal

the mixture

to

suspension

in

lamp

to

implied

platinum(I1)

were

predominated.

With

[42].

HF.

The

between

used

oxygen

as

the

under

platinum

high

for

of cadmium

illumination

aqueous

was

transitors

scavenger

dispersions

of very of

a

from an

coating

field-effect

aqueous

radiolysis

in

with

deposited

and

contact

solutions

the

to remain

a mercury

species

and

was

evolve

of

lutetium.

of a photoconductor

with

cells,

in which

study

coated doped silicon

H,[PtC&]

[PtC1,]2-

in a system

for

was were

solution

exception,

platinum(I1)

solar

a and

of

sorption

and

a titania

platinum(IV)

electrical for

MgO

of dissolving

irradiated

in

state

static

and exposing

on silica

reduced

or

chloride an

was the major species

loaded with noble retal oxides

polydispersivity

the was

consists

of a buffer

was deposited

'C to

silicon

both

In

cerium

a suspension

the bandgap.

deposition

PtCl*.

conduction

and

and

thiol,

was

[39]. of

1411. XPES of the platinum

an excess of buffer platinum(O)

acid

or

HzfPtCls]

in the presence

Electroless

pH

carbon

supports

SiOZ

dioxide

on

HZ[PtC16]

valence

various

[40]. A method

containing

alcohol

on

high

chemisorption

concentration

platinum

atom

of and

the

A1209,

oxides

properties

solution

on

sites

A

adsorbing

air

and

catalysts

monoxide

zirconium

adsorbed

platinum

in

platinum

platinum

that

metal

after

carbon

on

1361.

solutions

calcined

increasing

claimed

or polyfunctional

ethanol

of

I&[PtCle]

strong

preparation

hydrated

controlled

of wavelength

aqueous

said

per

aqueous

of

by reflectance

HCl.

+ iridium

for

hydrated

with on

is

adsorbed

in an

and a mono

that

decreased

was

then

increasing

[MCls]*-

metal

catalysts

light

with

However,

chloride

complex

of [PtCls]'-on

increased

was amenable

for the same surface

not

alumina

[NH1]ZIPtCla]

iW I z CPtCL I particularly considered [38].

capacity

was

of

acidic

on

activity

activity

and

In the sorption

were

drying

conditions

studied.

mixture

platinum

by

increased

has been studied

a

competed

H,[IrCl,]

material

in

of

or

obtained

H[ReO,]

hydrogen,

of

interactions

+ rhenium

was

either

Hp[PtCls]

all three components

platinum

supports

containing

with

deposition

adsorbate-support

dispersion

1333. The process

1341.

of r-alumina

[35].

determination

stability solutions

with and of

6

and acrylamide or ff-rethylolacrylamide (NMAM). H2rptclsl effectiveness of the platinum supported on poly-NMAM for generatlon

hydrogen

from

[Ru(bipy),]'+/MVz+/edtaH~ electrode alkaline

film

was

solution

contact

with

a

system.

formed

on one

plating

was

water

on

ion

activity

exchanging

side of the membrane bath

containing

low

the

[45].

An

allowing

an

the membrane

in

membrane

and

induced

using

was

by

to penetrate

Hz[PtCls]

catalytic

light

investigated

Specific

an

The

at

hydrasine

pH

5-6

[48]. The sorption occurred

by

of aqueous

first

substitution

of

order

the

were produced

Electron

nicrographs

by poly(etheneronosulphide)

kinetics.

hydrolysed

platinum

30-50 atoms

Hz[PtCls]

complexes

by r-irradiation of

sorption

The

acid

mechanism

[47].

of an aqueous

the aggregates

indicated

at 30-80

ligand

Microaggregates

solution

an

was

'C

of

of Hz[PtCls],

aggregation

number

of

1481.

Hydrogen

was

irradiation.

As

from

generated the

reaction

fell

The

[49,50]+

aqueous

proceeded reaction

TiClS/K2[PtCls]

acidic

the

Tic&

could

reduction

rate

solutions

with Ti"+, La"+ or Fes+ as a sacriffcial

was

consumed

be accomplished electron

donor

on the

and

in neutral [51].

the transfer agent in was shown to act as a chain HzEPtCl61 copolymerisation of acrylonitrile and 2-propene-l-01 [52]. Polyethyne doped with

or

Ptcl.

implied

that

doping was

[53]. Ptcl, titanium

H,[PtCl,] was

said

The

entropies

of

included atomic

including

[PdCls]*-,

Hz[PtC16]

and PdClz

DTGA techniques:

Hz[PtC16].6Hp0

on M[CO,]

were

in aqueous,

reduction

nucleating

used and

for

and products (M = Ca,

ions

propanone

Sr or of

and ethanol complexes

according

of Hz[PtCls]

platinum(II) the growth

reviewed;

Empirically of +

for

species

calculated complexes

coefficients

of

solutions

were measured using TGA and

to reaction

hydrolysis

studied.

(4) [58].

Pt

(4)

of platinum

[PtC&]'-

was

Kz[PtCla]/~~H/~2[COS]/KOzCC,H4C02K

group

extremely gave

a

[60].

with hexamthylenetetraaine the anion

of

was examined

Clp + PtCl* __3

Ba) were

to

for

[SS]. Diffusion

3.66 X by weight of platinum

[HMTAH,][PtCls];

been

1551.

of heterogeneous

Pyrolysis

have

XPES

material.

1541.

the estimation

[PtC14]'-

decomposed

agent

substrate

[PtClslZ-

Hz0 + HCl + PtC14 +

[59].

product containing Reaction

by a partial

gaseous

and

[PtCle]'-

Hz[PtCls]

The kinetics

composition

conducting

of a range of platinum

w

to react

electrically

on a hot graphite

polyatomic

charges

[57]. Therrolysis

slow

accompanied

[PdClb12-

effective

an

to be an excellent

carbide whiskers

discussed

halides

formed

and cation

(BETA) gave a species of were

connected .by N-H--Cl

7

hydrogen

bonds

been prepared 1.3.2

[61]. The species and characterised

Complexes

X-ray with

with

powder

those

of

spectroscopy electrode platinum A

Croup

simple

that

acceptor

in

structure

formed

0.5 M

K,[Pd(OH),] and

were

electron

on the surface was

Ei,[SO,]

mono

and

ligands 1

+

compared

energy

loss

of a platinum

[Pt(OH),]

rather

than

Complexes

+ of

oxygen

(SOpP}

complexes

have

Several

[65].

been

Facile

reported,

Trifluoromethylsulphonate were useful

This was was shown

equilibria

and Cs[Pt(SO,P)S]

groups also

(Pt(S03F)4}

bridging.

(6)) were studied,

bidentate

*

HSOIF

(1)

their structures

has been described.

[Pt(SOoF)s]'-.

in preparing

shown to

routes

including

is an

a range

to one

excellent

of complexes

(661.

HS03F

{HIPt(SOSF)s])-

yielding

with oxygen

(5) and

group and such species

Hz CPttSOsF)s

and

[63]. XPES

route to pure (Pt(S0,F)4)

reactions

both

of neutral

Na,[Pd(OH),]

the species

[Pt(NH,)s(OSO&F1))[CF$IO~]~.

leaving

have

ligands

analogues

of SOBF.

trifluoronethylsulphonate for

Cy or Ph,C)

[64].

to have a polymeric

contain

of

oxidised

synthetic

(for example,

donor

platinum

indicated

oxide

16

(R = Me&,

(621.

photographs

their

anodfcally

an excellent

[RPC1,12[PtCls]

and

{H[Pt(S09F)s]}-

+

[H2SOoF]+

(5)

[Pt(SO,F)s]*-

+

[HzSOSP]+

(6)

*

(2) with

were not specified

&

platlnun(IV)

have

been

synthesised

but

[673.

OH R

0

The platinum

oximes

(1)

R = H

(2)

R = SOSNa

of

(3)

2-butanone

in ug quantities

and

4-heptanone

as [PtLLC1,]

and

have

[Pt~Cl,]

been

used

to

extract

[68]. The preparation

of

9 established

by

[(MeoPtC1}*] rearrangements state

than

shown

to

analysis the

be

independent

CPt(dmQ141 IPttSCN)~l (dmtp

shape

SCHZSCHZSCHZSCHt.

were

rather

band

complete

and

different

pivot

that

In

(6),

and

[77].

the

from

intramolecular

of

X-ray

one

transition

diffraction

thiocyanates

= 5.7-dimethy1[l.2.4]triazolo[l,5-a]-pyrir~dine)

prepared

Pt-Me

manifestations

rearrangements

showed

[76].

metal

data

on

S-bonded

were

[78].

Me(13)

d

Me(211 Mc(23)

(6)

Thiocaprolactam I or SCN). formally

However,

octahedral

of

llgand geometry

claimed, sulphur

structurally including

on and

the the

said

rather by

suggested

deprotonated

been

was

identified

structure

(Reproduced

with

to

form

1:l

confusingly,

the

authors

basis

of

group

crs-[Pt(retHzClz]C1

the

cfs-N,N

cfs-S,S

Octahedral

NH

complexes

had

[79].

characterised

from

only

the

and

[80].

The

t and

which

complex

and

coordination

to

[Pt(metH)s]C1a

involve

of

in (7)

have

an

have

coordination

((8). [PtL]C14,

complexes

to be

enolised

the

derivatives

of

appeared

The

trams-Cl,Cl

data,

Br.

(X = Cl,

[Pt(CSHIISN)ZXZ]. of

platinum(W)

Platinum(W)

[Pt&]'-

species

formula

IR spectroscopic

[Sl].

1771)

with

S,N-coordination

involved with

permission

of

rethionine.

been

prepared:

was

not retH.

In

the

10 latter

complex

positions

the

sulphur

atoms

of

the

S.N-chelate

occupied

aeridianal

[82].

S

JCL I

Ar

Ar

NH

(8)

(71

1.3.3

Chemotherapy

Cancer

Reaction Cl*)

gave

of

microanalysis, thought

c~~-[P~(NH~)~C~~],

IR and

to

be

reduction

due

lesPt

CPt(NH,),C1z(OH)z]

new

the

direct

[83].

noted

was

redetermination formula,

spectroscopy.

to

platinun(I1)

to

of

the

space

be

the

Plp/nnrc

group

the

of

Hz02

cis-platin

molecules

rather

Although

entirely

as a result

this

been

hemopoietic L1210 was

and

platinum(I1)

ISll. with as

of

diffraction

cause

H202

breaks

to give

its

PIP-DNA

were

CHIP

was less

C22LR

shown

to

[SS].

A

in nor

in vitro.

by

a

be

as

cells

in

vitro,

being

in the

suggesting

presence and

that

of

platinum(W)

and

was

of

more

an

CHIP

Pe[ClO,], both

initial

antitumour

the

sister than

FLAP

directly

or ascorbic of

CHIP

and

induced potent

a of

leukaemia

[issmPt]

showed Both

as dogs

against

tumours,

interacted

cis-platin,

to

this

reviewed rats

(FLAP)

CHIP

that

bonding

cis-platin

blood

cis,cfs.trans-[Pt(NH9)2CI,(oH)z] However,

as

[SO].

cis-[Pt(metronidazole)tcl,l CHO

been

mouse

in

decline

the

from

1871.

synthesis

profile

species

PM2-DNA.

mice,

active the

microscale

slowed

cis-[Pt(HtNCHMep)ZC1z] obtained,

has in

against

concentration/time

in

this

showed

hydrogen

radicals

studies

active

obtained

a

assigned

The

be

The

of

be

1881.

by

of

In

isomers

X-ray

complexes

Preclinical

it but

followed

exchange

reductant.

active.

cells

complex,

Neither

[88].

reported;

osteosarcoma

decline

chromatic

could

breakdown

agent

step

described;

rapid

species

of

platinum

vfvo

[84].

should

also

peroxide.

was

in

[85].

the

Pip/n

cis,cis.trsns-[Pt(HzNCHMe2)zC1+(OH)~],

CHIP,

chemotherapeutic have

the

than

or

HPLC of

by

activity

cis-platin

by

three

could

hydrogen

bridged

oxygen.

CHIP

with

than

or

(unspecified)

cis.cis,trans-isomer

cis.cfs.trans-[Pt(NHo),C1Z(OH)z].3H~Oz reaction

isomers

toxic

Br,

characterised

platinum(W)

the

of

(X, = H,O,.

were

anti-tumour

of

determined

structure

that

Xz

Their

of

iess

be

crystal

indicated

with

complexes

binding

One

to

could

data

The

nnr

either

cis,cis,trano-isomer

to

cis-platin.

cis,cls,trsns-CPt(NH~)zClzXz].

acid

which

were

complexes

must

11 be

reduced

viva

in

[CHIP].CH,CONMeZ [94] and

have

induction

complexes

fifty-three

tested

for

1.3-4

The

or

flash

were

more

studied.

volume

at

15

A

the

active

of

than

cis-platin,

and

showing

variations

complexes

Seven

or [95]

X-prophage

biochemical structural

action.

for compounds

(Y = halide

of nitropyrazoles

simple

effect

anti-tumour

was

It was

donor

others

in

of

the

were

less

very high or very

low

ligands

and

photocheafstry

The

short-lived

were

used

dilution

with

that

[Pt(NHs)4]Z+

or

reaction

of

[Pt(NHs)4(OH),]Z+

on pulse

radiolysis

complexes

11971. The

(7) was

site

The

determined.

electrorestriction

effects

[96].

b5 at 25 lC in a kinetic

for cytochrome

a binding

and

formed

platinum(I)

for

theories

as an oxidant

concluded

of

intermediates

platinum(II1)

infinite

consistent

were

PtU’JHs)sl’+ c-1

study

reliable

Group

photolysis

reaction

study.

[CHIP].0.5HPZ.

[93].

complexes

chemotherapy.

their

with

radiolysis

been

results

for

[96].

Complexes

have

platinua(II)

to

on

toxic. The test was most activity

data

have been reported

and

used

was

diffraction

cis,crsns-(Pt(H,NCH2CR'RzCH*N~~)Cl~Y~]

used

assay

platinum

as

platinum(IV)

been

also

X-ray

and [CHIP].HZO

such

Compounds OH)

[92].

of charge

-3 or -4 was

involved

*

[Pt(NHs)s]4+

The

+

[HO]-

potential

CPt(NHsIsWHz)13+

-

barrier

to

{Pt(NH3)*12]12

was

quasi-harmonic

approximation,

related

chloride

hydrogen

appeared

bonds

&rans-[Pt(NHJ).IZ]Iz

insufficient related observed. N-H--Cl

The

phase

hydrogen

25.2 kJ mol-' was taken [104].

suggest

bonds

structure

crystallography,

the

hydrogen

rather of

to amnine stronger the

existence

arnine

hydrogen

complex of

to

the

has

be

heat the

in

in

the

free.

The

and

stronger on

capacity

range

of

55-299 K.

to be 14.7 kJ mol-',

IlOZ]. phase

to correspond

rotation

to

The

bonds due

groups

determinations

over

was determined

for two of the four

for the barrier

[loll.

anomalies

NH,

method

barriers

capacity

view

shown

the

shown

higher

heat

calorimetrically

strong

were

of

(7)

statistical

essentially

rotation

x-type

changes

to indicate

The

very two

rotation

in having

this

measured

GO

quantum

was

to differ

to ammine

crhns-complex

a

and

confirmed was

barrier to

by

Experimental

[loo].

cis-[Pt(NHS)*CIZ]CIZ The potential

internal

calculated

+

to

ligands

However,

in

transitions the

the were

formation

of

11031. A value

of

in trans-[Pt(NH1)4C1,][NO~JZ

bonds between been

hydrogen

anion

determined bonds

being

and cation by

X-ray clearly

12 demonstrated The MerNH,

and

11053.

complexes Et*NH,

L,

and

c~s-CPt(NH~)rLzClzl~NO~l~

Me,N, were

Et,N

or

py)

characterised

[Pt(NH3)z(N0z)2]

with

were

by

phosphoric

(L = NHB. prepared

from

Me3CNH2.

EtNH2,

cfs-[Pt(NH~)ZC1,(NO,)*]

analysis

thermal acid

MeNH,.

[lOS].

The

reaction been

studied

z(NOZ) (NOI (HzPO+) (HJW,)l

(8)

(reaction

(8),

has

of

sic)

[X07].

Complexes been

cis NaI

or at

h-ans-IPt(NB31 X LA +HSPO.

v

[PtL2X4]

prepared

species,

-H*O

HP04

tl

CPt(NHa)z(NOz)

by

L acted

(X = Cl

two as

directly

which

on

gave

and

its

bulk

indication

binding

complex

of

of

of

and the

through

reacted

an

intramolecular

hydrogen

bond

ammonia

11121.

between

one

exocyclic

structure

heterocycle The

by was

complex

XPES. acting

have

been

The

paper

extent

give

to

L'

of

prepared.

mixtures

of

= (19)).

both

had

oxygen

a

Both strong

atoms

and

an

(10)

the

of

product

formed

It

was

concluded

as a donor

cis-Kz[Pt(N02)zC1~]

towards was

that

a

and lone

platinur(IV) prepared

reaction

on

poly(2,2'-1,4-phenylene)-6,6'-oxybis(3-phenylquinolaline)] investigated

and

platinum(IV)

been

(9), and

or

R

[PW7Cl,l

the

HOC1

(9)

The

of

gave (L =

the

or

have

techniques of

of

1)

octahedral

chlorine

diffraction

or

Either

[Cp,Fe]

measurements.

N(3)

rer-[Pt(NHS)z(L')C1,]

X-ray

pKa

with

Molecular and

(n = 0

complexes

of

by

ability

stoicheiometry

[PtLC14]

have

substituted

[108.109].

reduced

o-donor

of

imidazole)

alkenyl

N(3)

was

the

examples

bound

by

ligand

and

geometries

cis-[Pt(NH3)2(1-MeU)Cl].Hz0

characterised

2)

for

through

Species

or

first

mcr-[Pt(NH3)r(l-MelJ)Cl~].

were

on

IR spectroscopy

1-methyluracil

msr-[Pt(NHJ)2(L)Cl,]

bound

[Pt(EtNHZ)4][C101]Z

1

the

The

substituted even

cases,

ligand

CllO].

by

11111.

L = alkyl

all

inversely

n = 0,

characterised

little

oxygen

or

depended

(L = Hn(CH~CHpOH)3_n; prepared

Br;

In

a ronodentat&

frans-[Pt(RNHp)tC1,] rates

or

groups.

by

pair

of

H,[PtCl,]

of was

the

nitrogen

of

reaction

[x13] the

sequence

13 (9).

and

its

previously

structure

reported

proven

synthesis

by of

X-ray the

diffraction

complex

trsns-isomer

[114].

KzCPt(NCz)4]

100 'C cis-K,[Pt(NOz)z(SO.).l + RzCSCb] -

was

The

measurements. shown

to

give

anion exchange

resin )

cis-Kz[Pt(NOz)zC1~] Reaction chloride of

of

CPt(dmso)(en)CllCl

ion gave

the

product

monodentate

the

was

and

platinua(IV) determined

adopted

an

[Pt(phen)p(en)][Pe(CN)s]

in NaX ionic

298 K

investigated.

outer

was

shown

constants

and

hydration The phen)

the

were

X-ray

a

linear

the

ligands

oxidative

diffraction

study

nitrogen

of

of

the ring

essentially

stereospecifically

platlnum(IV)

complexes

of

ligand

coordination

formed

(11)

was stated

was passed

0.1

the

and

was of

aqueous

0.75

calculated

first

radii

(L = en, of

X,

1,2-pn. to

was for

association

and

heats

of

1,3-pn.

bipy

or

[Pt(edta&

was

a

[116].

were

derivative

new

chiral number

A

activity

prepared

from

to be through

revealed

of

[117].

and

that was

been

acacH.

In

the

formed

platinum(I1) have

An

and

prepared

(1191. urea

the aalno

on the unfavourable

)L]X,

synthesised.

centre

2,3-dinethyl-2,3-diaminobutane

was

ligand

solubility

to zero ionic strength.

between

pyrrolidine

and were tested for their anti-tumour The

structure

[llS].

addition

the

Ben

were

crystallographic

trans-[Pt(edtaH,)LXz]Xz by

The

The

between

constants

correlation

of

acid

I. Br or Cl) containing

varying

association

the

[115].

in which A is 1,2-pn or aminomethylpyrrolidine

coordinated

comment

diffraction;

(X = Y[ClO,],

reciprocals

prepared

[Pt(Hen)Cl,].nW,O.

conformation

(9)

hydrochloric

(n = 1 or 2) and extrapolated

be

of the outer sphere species

[PtACl&] X-ray

to

by

strengths

sphere

4-n)+

(Pt(phen) r(en)Xd( There

and

concentrated

complex

extended

solution

at

with

the

and

nitrogen

ten-membered

groups

only,

ring which would

(PtLCL] and no thus be

[120]. 5

/

H-N-C-N=C. L

)

H2N-C-N=-_

\

! 3

(111 The

adsorption

[Pt(TPP)C12] absorption

with

changes

changes 35~s

and

flashes

decay

rapidly

kinetic at

behaviour

355 nn and

with

a time

produced

532 nm have constant

by

excitation

of

been

studied.

The

45tlO ps. A low-lying

14 ligand

to

to metal

charge

Oxidative

addition

(12)

(13).

X-ray

gave

diffraction

transfer of Xz

Complexes

[123].

was

account

The

and

identified. reduction

predicted

element an

with

by

reaction

or

theoretically from

CuXz;

approxirately

of

Group

[121]. Br or

X = Cl,

octahedral

it

complex

I) by

chemistry

PLATINUM

of

donor

to give

phosphine) was

lost

cis-products

and

,Pd(OCOMe)L].

have

below an

been 200

'C

analogous

although

the

[124].

lfgands

with

lisSn

[122])

Chlorine

[L(MeCOO)Pd(u-OCOMe)

I4

and

was

noted

from

(L = triaryl

studied.

confusing

Ht[PtClo]

1y5Pt

permission

[PdL&l+] was was

for

rather

to platinum(I1)

AND

with

therrolysis

was

but

1.4 PALLADIUM

The

(Reproduced

described

reaction

Mbssbauer

as

stoicheiometry

the

provided

Coslplexes

the

characterised

their

Elsewhere

process

1.3.5

of

and

(from

was

[122].

(13)

prepared

state

SnCl,

nrr

generally complexes

in

propanone

spectroscopy. clear

that

has

been

Numerous the

major

studied

species process

could

by be

involved

[125-1273.

COMPLEXES

one-dimensionally

WITH

MIXED

ordered

IV/II

mixed

OXIDATION

valence

STATES

compounds

has

15 continued

to

Theoretical resonance

be

Rawan

distinguishing

classII/III

equatorial

modes

spectroscopic

A method

to derive

quasi l-dimensional excitation

subjected chain

to

topological

(1331.

The

[1343.

The

with

of

Gaussian

the for

electronic a

allowed

platinuw(IV) X-ray

detected

direct

species

has

Rawan

band

are

predicted

the

data

also

between

rings adopted

reported

infra-red

for

the

band

[141J.

Simple

relative

The palladium profile

agreerent

equations

intensities were

applied

and platinuw(IV)

derivatives

Raman

that the palladium

species The

platinum(I1)

for related

excitation

suggest

spectra complexes

maxima

the

of

has been dimerised

corresponding

fror

Such

to

domain

the

salt

is

PKS

vibronic

valence

system.

reaain

of

in detail

this

structure

[135]. EXAPS of the linear

platinuw(I1)

and

obtained

for

of overtones tp

the

platinum

species

[139.140].

Electronic,

calculating

in resonance

dimensionless

Ranan

spectra with

have

band raxiwa

analogues.

the were

corplexes

This

have more delocalised

[Pt(en)r][Pt(en)zXz][CIO~]~,

{MZPt15).2H20

structures

palladium

intervalence

to allow

to be made;

Crystal

of en and 2-pn

had lower

insufficient

centres

[137.138].

of the related

than

containing

with the spectra measured species

symmetry

[Pt(3-pn)211Pt(3-pn)tXplEY32

species

a chair conformation

and resonance

been analysed.

effects

at low temperatures

by

(X = Cl, Y = [BP,] or X = Br, Y = [BP4J or [ClO,J) were

chelate

of

mixed

presence

the

[136].

diffraction

a distinction

the

considered

observed

of as

vibrational

obtained.

been

distorted

of

to

process

sywwetrlc

the locally

along

of

to size

state

theory and experiment

confirmation

those

{Pt(EtNH,)Cl,}.

also

changes

increased

and

excitations

band

localised

between

salt,

relaxation

Raran

strongly

sore discrepancies

and

like

whereas

reference

walls

in

near to the occur

complexes

the ground

complex

changes

adapted

elementary

lattice

this

been

domain

structural

electronic

red

Since

propagating

the charge

and XANES measurements chain

analysis. degeneracy,

or

intense

model

although

[132].

luminescence

consistent coupling

has

of Wolfram's

two-fold

govern

bases

crystals

solitons

wall motions

LCAO

fror

[129J. The wavenumber

increased,

particular

[128].

effective

from complexes

structural

Other

with

spectrum

theoretical

possesses

11303.

discussed

very

in which

coordinates

line

published classification

is

mode of such X-bridged

not

were

small

normal

been

method

corplexes,

only

excitation

did

data

has

of complex

this

chain

symmetric

the

review

to a single coordinate,

stretching

of

a

the problem

in which

totally

chain

wavenumber

The

II linear

borderline,

the symmetric

and

data;

spectroscopic

are confined

each of several

11311.

studied

have addressed

class

on excitation

the

widely

studies

and

would

valencies shifts

and

of linear chain results

in

good

at 80 K [142].

(M = K.

Rb

or

[NH,])

were

obtained

fror

16 and

Hz[PtC14] yielded

a

ten-fold WI

MZIPtIS].

rubidium

salts

distinguished

and

excess PtI*.

indicated Pt-I

a

of

X-ray

MI

aqueous

diffraction

structure

distances

in

studies

related

(2.715(2)

and

to

of

the

Wolfram's

3.205(2)

Therlnolysis

solution.

the

for

potassium

salt

and

with

well

potassium

salt)

[1433. The

preparation

and

[R,N],[Pt(C,O,),] conduction

have

properties

determined

properties

from

now

An

and

X-ray

anions

platinum

with

the metallic

compound as

a

underwent

a

by cation

ordering

simple

spectra

of

or

O
2 or

the

preparation revealed

of

structure.

2.5x10-'

Q-'cm-'

Many

Along E1491.

blue”

properties

and

a

The

complexes. visible

Pd

was

related

For

contrast

axis

on

isomorphous)

provided

complexes vary X-ray

derives

predictably

related

from

the

X-ray

data

this

is the

magnetically

for

i-8= 5;

The

crystal

[Pt4(NH4)m

structure

of

influenced Raman (x = 1

[1481.

in

M-M

study

a

columnar was salts

of

blue

data,

have

cis-diamsine also

been

valence magnetic

41CN0315.~Z0

they

spectra.

are

The

transfer

to be

been

which

also

prepared

[154].

The been

species

n = 3:

cc-pyrrolidone noted

the

structurally

related

y = 2, also

of

11511.

have

x,

essentially

bands,

fully

and

SCF

colour

distance

The

(X = NO,

n = 4.5)

mixed

described.

which

charge

[152].

has

The

conductivity

diffraction

been

optical

pyrimidine

(C4HsN0)4][PFB]2[N03]~.~=,

not

diffraction

IPt4(NHs)s(l-MeU)~7CNO~l~

y = 2,

could

resonance

reported

X-ray

intermetallic

characterised

X = NO*.

been

chemistry

(with

[X(NH,)ZPt(~-l-MetJ)ZPt(NH~)~X][NO~]Y.nEi~O Y = 3.

was and

[Pta(en)4(CSH*NO)

the

with

first

structure

In

Lio_ez[Pt(mt)p].2Hz0

temperature

have

complexes

intervalence energy

chain

a

11501.

of

for

the

form

[D~,N],zCM(C,XS),]

An

and

example,

assignments

to

regular

configuration

preparation

amnine

from

3.7-bis(dinethylamino)phenothiazan

temperature

spectroscopy

in

diffraction

reported: and

the

the

which

have

room

of

that

a-axis

symmetric

K)

eclipsed

vector

prepared

revealed

reflectance

described.

wave

Crystals

were

the

[140].

Pt)

lPtp (en), IC5H4NO14(NO21 (NOa1 I [NO312 -Y&O calculations

Fermi

[144].

to

complexes, or

Electrical

[145].

four-fold

type

the

the

along

(Tc = 215

platinum

report

paper.

diffraction

species

dimeric

at room

again

In

the

M = Ni,

the

semiconductors papers

"platinum

in

anions

of

diffusion

absorption,

Rb[Pt(mnt)Z].2Hz0

full

Li0_,[Pt(nnt),].2H,0

transition

Se;

value

face-to-face

symmetry.

Optical

a

(electrolytically)

experiments

X-ray

insulating

Peierls

X = S or

planar

also

of

dimercaptodithiolene

stacked

were

for

Lio_a [Pt(ant)zJ

[147].

the

by slow

stacked

Peierls

to

oxidised

in

scattdring

study

were

four-fold

be

regarded

related

suitable

diffraction

partially

described

[Cu(en)][NO,]p

[Pt(mnt)tJo*5chain

be

diffuse

[H~en]o.sl[Pt(CzO~)o].2H~0 Ht_e[Pt(Cz04)z]

been

could

X-ray

of

X = gZO. [153]. violet.

cis-Diarmine

17 a-pyrrolidone

green has been shown to be a non-stoicheioretric

pyrrolidone indicated

blue that

the

state increased The

and

Pt-Pt

blue

structure

was

A

wide

excess

entirely

range

of

that

suggested

the

oxidation

of

of

pyridone

was

2.5

The and

2.42

2

the

platinum

of the data

oxidation

[158].

epr

the mean

The

state

gave

the

"C

nnr

was

data Redox

free.

2.3 and

2.8. The

to anchor

the

[157]. 1.4-3utanedioic similar

site with formed and

species

large

included

rrans-cyclohexane

carboxyl

gave

blue8

a

used

Ph).

group

at N(l),

[lSS].

treating

between

proceded

oxidation

by

or

the

and

inide

these

that

with XPES and epr

and

cis-

platinum

concluded

amides

(R = Me

coordination

of

(L’ = guanosine)

CPt(NHalzL’lCNQ,l

acid

oxidation

Slow

[1591.

obtained

the carboxyl

occurred

spectra

It was

platinum

class IIIA compound

for platinum

of

In

cis-diamrine

and that two quite different

3).

coordinated

to be the

of

data together

been

or

states

corplexation

blue.

and

has

1,4-butanedioic

state

group.

These

of the "blue" complex

appeared

carboxylate

localised

Kz[PtC1,].

the function

oxygen (II),

1,

amide

formation

acids,

blues with

oxidation

and

spectrum

H2N(C=O)CHZCRzCHICODH

that

monoaride

erotic

2.20

the

inferred

amide

platinum

and

suggested

acid

a8

calculations.

existed.

amides

titration8

optical

platinum

(n = 0,

1,2-dicarboxamide

ligand whilst

decreased

that this was a Robin-Day

various

HzNC(=O)(CH~),COOH

aLLthOr

length

and

interactions

suggested

of

structures.

by SCF-&-SW

probed

the HOMO was almost platinum-platinum measurements

bond

tan

mixture

diffraction

(over the range 2.25 to 2.5) [155].

electronic

a-pyridone

pyrrolidone

X-ray

results. a mean

from

in some

closely

Again

platinum

substituted cases

at the

resembled

of the platinum

was

those

between

CPt(NHs)z(HL’)lCNo,l+

of first

true

guanosine

or platinum

blue [lSO].

(la)

X = Me,

(14lD)

x

= H.

"Dithiomalonaride". ~M(II)(HL)zIPtX~I. (16)

of

Y = H

(16).

Y

= NOI

HL. or

(15)

CPtfHzQ)Clz

and

nitrogen

1 D’tChs

1

reacted

donors (HzL

[ISI].

whilst The

cMx,1*-

with (17).

CM(iL),lCM(HL)tX,lX,.

the ligand acted as an S,S-donor,

sulphur

i15)

in'
(W -

give

to Pd

or

Pt].

In

there was a trans-array [Pt(HtL)C1,][PtCl,]

= N.N'-bis(2-arinobenzoyl)ethane-1.2-diarine:

and

18 H2Q = ~.~~-bis~2-(2-hydroxybenzaldimino)ben~oyl)ethane-l,2-diamine) prepared

and characterised

[lS2].

(16) 1.5 PALLADIUM(II1)

Palladium excellent

and platinum

have

been

at low temperatures. trivalent

species to

KrLi[MFs]

studied.

indicated

cubic

form

(PdFs)

octahedra

palladium(Il1)

The data

for

the

implied possibly event

MS-X,

[PtCl,]of

that

on

of

of

for

of

couplings

the cube

elpasolite

elpasolite

[164].

structure

at

K,Na[AlF,]

by magnetic axial

permits

which

law only

between

the

In i$ NaCPdl& ] 25 'C with structure

a at

reasurenents distortion

the

of an

the reciprocal

and

of the

stabilisation

transients

weak

was

the

photoexcitation and

platinum-chlorine

bond,

best

[1661. Sensitised

photolysis

of

with

performed

by

pulse

experimental

representation

in the

apical

[PtCls]=-

trigonal of

been

generated

Comparison

coordination

have

for

the

All of these have been proposed

[PtCl,]*-.

[PtCl,]*-. {PtC14]-

with

exchange

that the strong

calculations

and

short-lived

photolysis

indicated

subject

that

dependence

was characterised

characteristic

including

tetragonal the

the

from the Curie Weiss

with

face

been

of

[lSS].

Relativistic [PtClaJs-,

phases,

deviated

a

with

105 'C. 4d' low spin palladium

have

temperature

the diagonal

data

epr spectroscopy.

The

of KzLiEPdF6]

along

the

diaers

This was associated

structural

transition

M(III)-M(II1)

[lf33]. New

susceptibility

crystal

(17)

AND PLATINDM(II1)

review

M * Pd(III) magnetic

have been

[PtXs]'-

radiolysls W

was

(X - Cl,

direct [PtCl,]Br or

flash

or

spectroscopic

of the species

positions.

pyramidal

species as models

Thus,

generated, the

homolysis was [SCN])

data

not

primary of

a

formed

in a system

19 containing chain

aquation

aquation

or

osriur(I1)

also

The

efficiency

of

[Ru(bipy),j'+ process.

was in the order

to the different

Further

(Pt2}g+

{Ptz(O,XO,),}

[Pt&]-

in

of the

ligands

to form

which

led

propagation

could

to

of

a

chain

in turn be related

intermediates

of the type

[167].

the

techniques.

[PtX4]-,

X = Br > Cl > [SCN], which

abilities

[X,Pt--X--PtXJ3-

gave

units

results

have

being

arrangement

been

characterised

sllllnarlsed below

had the Pt,OzX

by

X-ray

[168,169].

rings all bent

diffraction

In all

cases

the

in the same direction

to give C,h symmetry. r(Pt-Pt)/A

Complex

XtIPtz(SO4)~(HzO)tj

2.461

Naz[Ptr(HP04~4(H,0)21

2.485. 2.487

CCsRsNH]zIPt2(H2PO~)z(HPO~)&lz].HzO

2.529

C3.4-Me&sHoNH12CPt2(HPO~)~(3.4-Me2CSH~H)21

2.494

In

the

reaction

diaerisation was slow. complex

of

(18)

then

suggesting

crs-[Pt(NH,),(H20),]*+

the platinum

was formed formed

that

platinur(II1)

of

ft

complex,

initially

had might

an be

as monitored

but rearranged

average

platinum

coaposed

and three platinur(II)

with

of

centres

two

[P0,J3by 91P

at

nmr

to (19).

pH

l-4

the

spectroscopy.

The blue coloured

oxidation

state

of

2.3,

units

(19)

with

one

of

[170].

I HO--+--O 8

Treatment platfnum(II1) XPES and X-ray

\

pt IN”3

t-i 0’ 2

‘N”

3

yielded the (HL = MetCHCStH) rfth iodine CPttL.1 characterised by *H and *'C nmr spectroscopy, direr. [Pt,L,I.], of

diffraction

11711. Reaction

of pyrirldine-2-thione

(PylS) with

20

[PtYI,]'_ in the air gave the platinun(II1) X-ray

diffraction.

absence dimer

The

of air. This

formed

quadruply

reaction

distance

bridged

as pop derivatives

by o,o-donors

and

detailed

acid proposed appears the

sale

of

the species

to be a misprint claimed

the

React

ion

of

2.782 A

is shorter

lay

those

found

identified

isolated

in

the P.P

in

by the

of a platinur(II1)

a platinun(I1)

between

with permission

reactions

values bridged

complex.

The

for diaers species such

of

from [172])

[Pt(NHS)2(N0,)z]

with

INH,12~Ptp(HP0,1z (HzOlz] to be formed, in the text the

and CNH41tEH4Ptr(~-Po,),(Hzo),l. somewhat unclear 11731.

[MePt(pop),PtI]*-.

<20). be

[172].

study

subject

direr. could

of the formation

of a ligand with

(2.554 A)

(ta) (Reproduced

A

bridged

[Pt(PyuS)*J

is the first example

by direct

platinum-platinum

intermediate

at

this

point

phosphoric though

[107]. Another

there

paper

on

intermediates

CH,Pt(III)(NH,),(NO,)(NO)(PO.),l the characterisation of these species being

Me1 with gave fPt2(PoP),l*(POP = CPZOS&]=-) characterised by X-ray diffraction. The Pt-Pt distance of than

in

[Ptn(pop)4]4-,

but

exceeds

that

in

the

related

complex (2.895 A). The strong tranr-influence of the methyl rPt(PoP),Clz]*and iodide ligande was evidenced by the red shift of the doui,* transition relative

to {Ptz(pop),ClzJ4-

[174]. The photocheriatry

of

[Pt2(pop),XZ]*-

has

21 been

investigated.

accelerated The

halogen

substitution

first mononuclear

diffraction

was

paramagnetic

could

Cl% (PoP)4xYl'-

(21),

complex

prepared

by

photochemically

11751.

platinur(II1)

prepared

without

be

by

species

reaction

to be characterised It

(10).

platinum-platinum

was

bonding

by X-ray

a stable

deep

blue

[176].

Xz or TICll [Ru~R]zfPt(CsCl5),]

(101

EBu,Nl CPttCtsCls )a I

)

(21) 1.6 PALLADIUM(I1)

The

relative

studied waves

AND PLATINUM(I1)

using

stabilities

in solutions

values

of

perturbation containing

is difficult

cis-

theory

and

trans-isomers

11771.

more

than

and the problem

The

one

was

of

separation

type

tackled

[PtLrC12]

of

of metal

was

polarographic

ion with

by differential

close

&

complexation

11783.

1-6-I

Complexes

The

with

changes

properties

(1791.

chlorine

under

absorption

Reaction

and

their

palladium.

were

ligand

studies.

metallic

390t5

of

synchrotron

alumina

from

[184].

Active

PdCl,/HCl. monoxide immiscible

of

the

shown

at 301-620

chloride

carbon

dried liquid

and

ion

retained

[165]. phases

The

the

PdCl= a

on

or

treated porous

distribution

in the AlBr./HBr

found in the

of

near PdC12

with

and narrower

heat

The PdC4

of a ds metal

compared

as 167~17 Ja01-~

was

[lSO].

compound

capacity

the transition

concentration

in

The

molecular

absorption

spectra

a higher

[1823.

PtClz

states

the

biological

with

The structures

results

and

their

chain

In X-ray

K to determine

silica

the

to Dzh MO

to have

containing on

to

gave

of

absorption

and

metal

platlnum(II)

filament

1300 K

[ZSl].

L-edge

palladium

solutions

filter

at

related

radiation

PdCl, was than

by DSC

effect

of related

a crystal

field

'C and the heat of transition

The

be

platinum

conditions

anisotropies

(XANES)

was measured

glowing

spectra

planar

with

states

a

may

at 1-11 eV at low temperature.

obtained

unoccupied

derivatives

geometry of

reflection

rhombic

structure

lfgands

chloro

their

equilibrium

and

in a

of

in

have been measured spectra

donor

17

photoexcitation

consequent

ion

Group

edge were

those

for

density

of

of cr-PdCl,

temperature

of

[183].

the

adsorption

PdC1x/AICIS with

container

a

was

for

use

of

PdBrL

system

studied.

on

investigated

solution

behaviour was

of PdClz

containing as

a

carbon

between [Pd2r,]z-

the was

22 the predominant

palladium

The reduction good

catalytic

suggested energy

of

of PdCL

the

Kinetic

species

reduction

by

surfaces

for

catalysis

solution

for

for printed circuits PtIz aqueous

was

of

the

deposition

catalytic

has been determined

unstable

palladium

(1891.

for the activation metals

could also be coated

active

The

contained

use

powder

of

of metal

followed

PdCl, /SnCt

conductor

in

patterns

[lSO].

by reaction

[1911. The crystal

activation

of

systems

with

an

solution

deposition

deposition

palladium

spectrophotometry

with

intermediate

a dry catalytically

has been reviewed

synthesised

ethanol

An

electraless

with

[186].

'C and

[Pd(drf)zC1,],

[188]. Insulating

by pretreatment

PdClz/SnC12

alkaline

was

70-90

[187]. An aqueous

PdClp/HC1/MeC(OH)(PO,H),/SnC1, with metals

at

110 kJ q ol-'.

of

in both phases

dmf gave highly disperse

studies

reduced

complex was postulated

non-conducting

species

in aqueous

activity.

that

for

carbonyl

containing

of H,[PtCls]

and molecular

by X-ray diffraction;

with

molecular

structure

of

the iodo bridged

iodine

in

[BudN]z[PtzIa]

anion

was planar

[lSZ]. The adsorption been

described

zirconia

was

of

(PdC14]+-

[193].

The

on alumina

sorption

investigated.

of

The platinum

Na[OH] and 0.1 M NaCl. with palladium The

electronic

methanol largely

absorption

or ethanenltrile assigned of

separation platinum

rl(*Azg)

for palladium

were analysed

by quantum

in reactivity

between

"Cl

NQR

and

spectra.

XPES study of Cl,

[SCN]

X-ray

[NCO])

Analogous

diffraction bonding

[Sl]. A

[HMTAH]a[Pd&ls] Microgram acridine

be eluted

using

spectra

for

has

hydrated 0.1 M

states

measured

and

was

to explain

greater

for

species

dependence

of the

(M = Pd or

to the reorientation

of N-H --Cl hydrogen

the

the difference

[(H2N)&],[MC1,]

may be attributed

that

of these

[197]. The temperature for

in

suggested

spectra

in order

[PtCl*]2-

have been

[PdCI,]2-

excited

and reformation

bonds

of

[198]. An

(M = Pd or Pt; X = [C(CN),]. [N(CN),]. [QNC(CN),]. that the pseudohalides withdrew electron

from the retal

data

between

structures

tetrammine)

on

electronic

methods

pellets

KZ[PtC14]

suggested

density rost effectively hydrogen

CD

for

rs('Bg)

The changes

could

in methanol.

'Ii nmr T, values

[PhbP]2[MX,]

or

and

and n-alumina and

later with 2M HCl [X94].

of data

the complexes

the cations with breaking

eluted magnetic

[lSS]. The

chemical

and the

Pt.) has been reported.

complex

[PtBr*]'-

[195]. Comparison

the

than

and

fibres

KZ[PdC14]

were

for

the

centre

salt

the NH: group proposed

related

[PhCH&H(CQQEt)NH,],[PtCl~J

and the chlorine

for

complex

[ISQ].

[HMTAHz][PtC14]

of

palladium

was

of

[PtCl,]*-

showed [ZOO].

(HMTA = hexamethylene prepared,

as well

as

extraction

of

[ZOl]. quantities

orange

of

palladium

tetrabromopalladate

could from

be

dilute

determined Hr[S04)

by into

3-•ethylbutyl

23

and

ethanoate/propanone. Imipramine

tetrahalopalladate

determination

of palladium

characterised

by

theobromine)

have

against hooded

also

DSC

spectroscopy, conjugated

LR

forms

[207].

The

also

used

[ZOS].

12061.

reactions

for

ether)

of

530 nm

{202].

spectrophotometric [204].

were

prepared

and

[LHZ]t[PdC1*]

(L = theophilline

and

by

studied

fNH4]2[PtCll] to

elicit

a

moiety

was

IR

and

in

free

and

directed

conjugates

iodoethanoic

addition

or

'Ii nmr

antibody

of ovalbumin

of oxidative

and

used

specific

iodorethane

the products

at

[PhCIi,R(Ph)Me,][PdII]

isolated

or the platinum

[PtC141z- were studied;

fluorescence

(L = crown

walbunin-Pt

free platinum rat

TGA

the

were

[203] as was

been

and with

of

salts

WI aCPdCl,l spectroscopy

complexes

The

measurement

in the

acid

with

were characterised

[206]. The interactions and [Pt(SCN),]*Three platinum hydrogen in

of methyl

cobalamin.

have been studied

binding

production

MeB,.,

with

by *II nmr and W

sites could be identified

from

the

catalytic

[PtC141Z-,

[Pt(CN)&]'-

spectroscopy

in solution.

[ZOS;. The quantum yield

photoreduction

of water

was

for

measured

the

[Ru(bipy)lCl,]/[Rh(bipy)~Cl~]/N(CH,CHZOH)~/K*rPtCl~] system using a 3actinometer [210]. radiation induced reduction of The [Pe([email protected],) 31 5-brono-6-hydroxythymine to give thymine was promoted by transition metal salts

including

operate

Kz(PtC1,J.

1.6.2 coaplcxcr

Group

with

1.6.2.X Unidcntatc Thermochemical been derived Water and

for

exchange by

in

pathway

was

assumed

to

The

for the exchange.

thermodynamic

that for the platinum investigated

[Pt(Hzo),]'+

monoxides,

including

data from the literature

of

was

the

studied

linewidth

parameters

thus

The exchange

analogue

or The

A’-

products

the signal

derived

and

implied

an

[OPO,H,]-,

"0

n

(reaction

characterised

=

nmr

associative

times faster

or 4; Am- = [ONOz]-,

were

have

of temperature in the

of [Pt(&O),]Z+

=

PtD,

12121.

rate was 1.4 x [email protected]

n = 1,2.3 2;

PdO

as a function of

[213]. Anation

(Am- = Cl-,

n=l A=- = [OSOl]'-. 3: AnI- - [OCOCH~]-. n = 1). spectroscopy

lfgands

donor

[Pd(HzO),]'+

measurement

mechanism

The

transfer

llgands

gaseous

from experimental

pressure

been

electron

16 donor

oxygen

data

spectrum.

has

An

12111.

(11))

n = 1.2 or

1.2.3 by

than

or

4;

lssPt

nmr

C214].

+

~Pt(A)n(HzO),_,J~z-mn)+

r&A-- -

hydrolysis

of

Pdf+

in

aqueous

media

has

been

studied

24

electrochemically. concentration NaCl

At

a

specified

of Pd'+ and decreased

12151. The electronic

contracted

GTO

the first

basis

bond were analysed M[Pd(OH)4] X-ray

sets.

coordination

of {MR+-OHz---OHZ}

complexes

effect

of the charge

on the hydrogen

(including

by using double-zeta

and

bonds

of

the composition

as well

of

as the W+-OHz

[ZlS].

(M = Ba

diffraction

or

Sr)

powder data

and isostructural. Anation

The

the

in the concentration

by the CNDO approximation

sphere

with

increased

with an increase

structures

that of Pt*+) were calculated

hydrolysis

pH

was

Therrolysis

of

the

prepared

implied

from

Na,[Pd(OH)4]

that these complexes

gave successively

MPdG(OH)*

and

and MPdOt

f217].

cis-[Pt('SNHs)t(OH,)Z][CIO~]Z

complex

H(OH),.

were orthorhoebic to

give

(z-m)+

l"Pt, lSN and, for cis-[Pt( ‘5NHa)zAtoH,)l was studied by s1P nmr spectroscopy. Reaction with [NOB]- gave successively

Am- = [H,PO*]-,

cls-[Pt(NH,)t(OH,)(ONOZ)]+ identified Both

ethanoate

on oxidation

could

[Pd(Nh

141

[=Ql.

thermal

palladium(IE) Palladium

complexes

analysis

structure

of

A

film

platinum

photodissociation dithiones

of

related [ZZS].

of

NapCB4073

I Na2[S04]

The enthalpy

nitric

by oxidation and

bonding

multidentate

oxygen

12251.

alcohol

Included

was

metal

12223.

The

was determined

by

triangle

each pair of palladium and platinum

salts

of electrically

12241.

donor

on

ligands

quartz

plate

by

complexes

of

diones

a

Metal

removed

of

[221].

of an isosceles

[223]. Palladium

deposited

laser

and [W(acac)Z]

These

acids

benzene

between

such as glass

or

study

of palladium

ethanoic

from

bridges

by

spectroscopy

spectrophotonetric

A

acid were used for the preparation

of sublimation

better

or

by IR and electronic

as crystallised

[Pd(hfacac)*]

Polyvinyl

converted

salts have also been used,

to acacH were used for stabilisation

colours

been determined.

was

were

ER3NH]tEPd(NO3)* 1

respectively

two ethanoate

and

which

be

complex.

the presence of [Pd(HZO),(HSO,)]+

on insulators

Bidentate

could

sulphate

trioctylaaine.

and ammonium

[220].

atoms, but no palladium-palladium

1.6.2.2

dirers

study. The {Pdj) unit consisted

atoms with

coatings

by

characterised

mixture

of 7,13-abietadiene-18-oic conducting

both of which

unidentate

bridged

could be synthesised

a

[{Pd(OCOMe),},J

an X-ray diffraction of palladium

as anines

methods

ethanoate in

anion

a

[218].

in H,[SOI] revealed

oxide

nitric

Other

gave

extracted

be

nitrate,

and the extracted

by

gave

to platinum blues

tetraoctylammoniun

and

[SO,lz-

and phosphate

Palladiua(I1) hNlt

and cis-[Pt(NHS)z(ONO,)z],

spectroscopically.

from

of photographic waste

water

by

using and image adding

(M = Ni. Pd or Pt) [227].

of a range of transition [Pd(acac)r]

(+ub25e

complexes

has

= 132a17 kJ sol-')

metal

and

25 [Pt(acac)=] also

(&Hgub"a

discussed

and

[228].

dodecane.

factor

partition

these

was

PTIR

recorded.

spectra

For

spectrum

coefficients and/or

cavity

benzene

A

from

The

a

Tesla).

The

the

diffraction;

of

steric

this

identified.

In

a-aryl

species.

(24).

It

Reactions Pd-PPh3

is

the

(a),

and

(13)

The

B,

1

an

hydration

major

was

also

product

EtBAl

The

the

with

with

pathway

palladiur(II)

titrations

and

IR

complexes

charge

its

substrates static

for

quenching constants

systematically

with

spectroscopy;

transfer

was

ligand

and

catalytic

and

related.

a

(29)

complexes

of

a

to

be

so but

of

the gave

O-bonding

stronger the

than

the

products

related with

the

related

species and

X-ray

was

system

a

was

variety

evidence

of

for

the

[235].

(and

of

in a

reacted

of

acac

by

4-pyridyl)

favour

was

although

tenuous

further

Reaction

or

of

(14))

only

no

to

of

other to

described

containing

the

of

according

curiously

arsenic

properties

complexes

aluminium

ligand

as

ligands

and

to

was

proceed

(2371.

complex

(28)

bond

IPd(acac)zJ

acceptor

3-

might

= (25))

phosphorus

[232].

behaviour

the

gave

complex

was

[ZSl].

spectroscopically

80 %

Pd-PE&

(26).

rather

reactions

electron

an associative The

was

transfer

{Pd,(tribenzylideneacac)3) to reflect

(HaH

platinum

both

ppm

data

characterised

(R = 2-,

(reaction

[Pd(Ha)t]

was

field

at

10.000

proceeded

ligand

fluxional

substitution

in the

[236].

and

the

ca.

observed

EtSP

[Pd(Ha)(Ha-C(3))Bl.

of the of

that

of

and

CSA

relaxation

nmr

shielding

K)

by

were the

the

(2-MeC,HI),P

tfacac

o-aryl

and

dominated

13C

(22)

than

in

(295-353

reaction

more of

the

6('s5Pt)

time

with

be

excess

with

lssPt

could

of

confirmed

12341. give

reaction

Scheme

quenching

The

L = p-diketonato)

from

unidentate

that

Halide

to

resulted

form

determined.

Pt;

was

ligands.

isomers

spectra

investigated

related

water

or

for

derived

the

extent

with

(12)

metals)

via

were

temperature

The

first

the

considered

stereochemistry

said

between

but

relaxation

time

of

two

was

[233].

ligands,

bulk

to

bond.

discussed

The

were

[Pd(acac),]

relaxation of

[Pd(tfacac)Z]

solution

predominated

also

complexes

energy,

correlated

[Pd(tfacac)(tfacac-OI(PIC,H,-2-Me)a)]. of

Pd

anisotropy

correlation

reaction

he

function

shielding

the

(M = Cu,

spin-lattice as

9.4

strengths.

calculated

(22)

of

formation

could

"'Pt

analysed

and

(4.7

[ML,]

v(M-0)

The

were

strength

of

[PtL2]

[230].

anisotropy

because

8-Hydroxyquinolinate

[229].

The

field

The

kJ mol-l ).

tetrachloromethane

determining

important

= 133~9

first the and

(27), chelate

were with

also the

sould

studied

was

assumed

[239].

(28)

acceptor

lhe

in

for a

affinity

of

inferred

the

pHmetric

[238]. was

The

shown which

to are

characterisation

matrix

thus

be

by

molecules,

method

luminescence

electron it

was

structure prepared

ArNOz

hydrogenation. order

[PdL=].

at

77 K.

acceptors that

The were

molecular

26

complexes

were

complexes

of Arnebin

derivatives

formed

12401. I. (30)

A

polymeric

structure

[241]. The stability

of (31) in 1:l and 1:2 stoicheiometries

(22) (Reproduced

with permission

was

proposed

constants

were determined

from

for

metal

of palladium(I1) 1242).

12321)

R’ R +

‘Pd’

E$P

Ph3P’

Tl [R*C(O)=CH-CRY]

Et Rp>W
l

3

X

PEt3 + -y

9

PPh3

27

R’ R,

TI[RkO)=CH-C(=O)R’l

/_Yh3

+

>

TIX

+

(131

PPh3

Ph3V

Tl [acac 1

/R

+

TIX

+ PPh3

3

0

0

R&l

+

-

[Pd(acacIzl

R,Al(acac)

+

(RPd(acac))

,\r;l

{RPd(a/

RpPd

(acac)Pd--Pd(acac)

R,Al 1 R,Al(acac)

Scheme

1 Reactions

of

[Pd(acac)sJ

+ R,Al(acac)

1. Pd(0) + R-R + Pd(O)

with

alkyl

alanes

12361.

(14)

28

& 0

OH

I

0

(27)

l3r

HO

EPt(C204) n12supercritical preparation

inactivated

contrast

non-isomorphic.

occupied

were

from other chelates

KZIPd(CIOd)r]

carboxypeptidase; within

to the reactions It was

separated

[242].

was

used

using

in

the

layer (2441.

close to the 2nz+ cofactor

considerable was

CPd(C,O,),lzchromatography

of a photoimaging

K2[Pt(C,04)*} site

and

fluid

thought

binding

the enzyme of Kz[PtC1,].

that

four

occurred

active

at a single

site. This was

the derivative

distinct

binding

in

of which

sites

were

in this case f245].

on photolysis or theraolysis. palladium metal, CNH4121Pd(C%Ol) pl yielded, ammonia and CO,. Under thermal conditions the Pd-N bond was the first one

broken. [246].

but

under

a

photochemical

regime

the Pd-0

bond w%s

first

cleaved

29

Reaction other

of (EtO&)&R, the

compounds,

diffraction

with

in basic

[PdCl.lZ-

structure

the

of

complex

solution

being

gave 1[32), among

elucidated

by

X-ray

[247]. (C (COOEt12)2

[(Pt(OCOMe)(OH),(HZO)}6] S-bonded

[248]. The

(33),

in which

structure

was determined

by X-ray

platinum

dihydroxyarene

complexes

[249]. New steroidal Their

prepared.

was similar

in dmso

biological

gave

effect

to that of cis-platin

with

dihydroxybenzene

3.4.5.6-tetrachloro

of

Reaction

on the huaan

the

dmso

ligands

diffraction

were

techniques

such as I[-) have been

breast

tunour

cell

line MCP-7

[ZSO]. Cl Cl

0

Y0 (d mso)2Pt -----a

Cl

+ Cl (331

(34)

A

series

[Pt(bipy)L]

of

benzene-1.2-dicarboxylic acid) were AgCNO.].

prepared

Their W

antibonding

acid,

by treatment

spectra

orbital

showed

of the bfpy

(l&L * 4-Me,C-1.2-dihydroxybenzene.

complexes

acid

2-hydroxybenzoic of

[Pt(bipy)Clt]

CT bands

2-mercaptobenzoic

Na*L,

fror a platinun

as well

ligand,

with

or

with

d orbital

as ligand

or without to the r*

to ligand CT bands

12511. Reaction

of

[Pt(PPh,){P(CMe,),)(o,)l. to

give

(35).

observation.

though

not

the

commented

MeOtCCwCCOIMe mechanism

of

molecular

with

CR,Pt(PPh,){P(Cne,),)1 could the

on by the authors.

be inserted process was

was

that

into

oxygen the OZ

unclear.

A

gave ligand curfous

the srP nmr .spectrum

30 of

(35)

and

its

precursor

phosphorus--phosphorus phosphines expected

apparently

(2523. Treatment

product

the

of [Pt(PPhS)+Oa]

(36) by reaction

for the reaction

showed

despite

coupling.

was proposed

but

phosphorus-platinum obvious

inequivalence

with Me&CCE&COC&C&Me

at the carbonyl

group.

A detailed

not

of

the

gave

the

mechanism

[253].

COOMe

(361

(35) study

detailed

A

orthophosphate. using

initially

important

and

gave

as models

with a

to

DNA

of

triphosphate

activation

complex.

of phosphate

exchange

chelating

ligands

mechanism

involved

which

the

drso

‘Cl

sulphur

of

free

LL

in

was

a

and

Such

such as

and

((m)).

reactions

hydrolysis

and

are

of

the

dmao

by

oxygen

donor

bound

dmso

dissociation

n2-bonded,

A_

O-

fPhtPt(dmso)zJ

true

products

to
0

:: -P-O-LO-LOI A_

ty’

The

undertaken

[254].

Hp'P*P

Ambidentstc

been

containing

0

1.6.2-3

has

cyclisation

blue

with

cfs-[Pt(NH,)zC1z]

anions

phosphate

subsequent

platinum

of metal

of binding

reaction

Monodentate

formed,

also

Orthophosphate

mechanisms

the

pyrophosphate

31P ntnr spectroscopy. were

(37)

of

followed

has

ligands

and

been

to give by

the

replacerent

investigated. Initially

competition

for

of The

reaction

[PhzPt(dmso)] the

in

intermediate

31 between

R’R*SO

The

rate

to give was

very

increasing

sulphoxide

associative

intimate

controlling

step

An the

X-ray

dmso

hydrogen

accounted

by

Oxidation

OP

and

the

or

easier

[PtCt

an

p-

at 25 'C.

decreased

with

and

L’.

dmso

with

asynchronous

atom

There

liganda, but

by

two

solvent

studied.

sulphide

in the rate

Pr,SO

solution

diminished

that

drso

wlecules

were

of crystallisation.

which

to

dmso

were

to

the

previously

(40)

gave

in

a

only

complexes

The

or OS(CHz)&) sulphoxide

mutual

replacement

as

[250].

with

a

12591.

such

isonerisation

be

The

could not be readily

made

complexes

showed

intermolecular

appears

which

complexes

Et,SO.

In

which

q echanisa

stabilised

than in [Pt~en)(dmso)(HzO)]*'

bound

polymer

rate

was

the two dqso

(L.L' = dmso.

associative

but

as the attacking

being

trans-effects,

[{PtLC1(u-C1))2] a

effects

consistent

third

were

tranr-[PtLL'CIZ] at

between

in rethanol

trans-[Pt(HzNCHMet)(dmso)Clz]

crystal

cis-dichlorosulphoxide

S-bonded

occurred

was

[Pt(en)(dmso)z][PPs]z.

between

cismuch

[Pt(en)(dmso)12+

of

the

replacement

effect

for

studied

electronic

with.oxygen

study

In

[258].

drso

labilisation

been

(2571.

to platinum

of

to

This

bulk.

mechanism

S-bonded,

bonds

S-coordinated kinetics

sensitive

diffraction

was

have

[Pt(R'R'SO)Cl,]-

mt

of the reaction

The kinetics

dmso and LL [255.256].

and

prepared

Prom

cis/trans-mixrure supporting

bulk,

an

[ZSl].

(40) *he

nature

[{PtL'(OH)X}t]

species and

were

and

X-Cl

Acidity

either

exerted

sulphides

constants

decomposition,

oxy#gcn

compfexes

providing

Br).

have

(L = R2S.

a stronger

a

It and been

R2S0

cis-effect

or

was

prepared

by far

concluded

oxygen

ators

determined R,Se:

complexes

IR spectroscopy

that

the

bridged

for

R = Me,

on the dissociation

hydroxy

in the

Lz

[Pt(en)L(H,O)]*+ Et

or

Pr).

constants

The than

[2633.

sulphvr

oP

investigated

complex

L'

or selenides.

f-6.2-4 Bidcntatc Palladiua(I1)

was

or

in the

[Pt(l,2-pn)L(H,O)]*+

sulphoxides

in

H,[{PtL+(O)Cl},]

bridging

(2621.

bridges

the

Lf = dmso.

(L1 = Et&SO, groups

of

donor

ligands

(41) sublimed useful

particularly

method

for

easily

and without

purification

[264].

32

Thiocarbaaide

complexes

R = substituted and

characterised.

thiocarbamides

cW(RNWC(-S)NHC(-O)Ph)Q~]

aryl. HQ = benzene-1.2-dicarboxylic IR spectroscopic

data

(M=Pd acid

indicated

or

Pt.

inide) were prepared

S,O-coordination

for

the

[ZSS].

(41) The

precipitation

1-hydroxy-2-pyridine compared shifted with

with

the

to lower

The

related

acid,

exhibited

1.6.2.5

Its derivatives

have

o,O-chelates

the

[267].

metal

chelates

of

been

investigated.

When

pR dependent

precipitation

was

[ZSS]. Palladium(II)

some

M.~ltidcntatc

Reaction a tridentate quite

the

formed implied

2:3 and

1:3 complexes

sulphur

and possibly

0

(HL = H,NC(-S)NRN-C(Me)COOIi) was prepared from EPtLzl The ligand acted as an S,o-chelate and the geometry was trans.

that of the free ligand

are

of

complex

complex

compound,

and

extraction

(42). Ir spectroscopy

coordination

[NH4]2[PtClsJ. The

thione

pH values

thiobarbituric

also oxygen

and

oxygen

O.S.N-donor

well

known

sulphur

nitrogen

but

and

numerous

donor

gave IPdI.(bOIl

12693. Ligands

represents

R’

activity,

this

was

lower

than

[268].

of PdClt with I&L. (4R),

(U), HO

antibacterial

acting

complexes

an intermediate

type

ligands

i n which [LIZ- acted as

as N,O,-donors have 12703.

been

or NsS.-donors

prepared.

The

new

33

Complexes studied.

of

In

unprecedented established

(45).

characterised

by

X-ray

binding

of

the

N(3),C(4) men

(2711. ligand

two nitrogen

atoms

from

derivative,

the most

likely

occurred

and

ethanol.

1.6.2.6

salicylaldoxire described;

oxygen

nltro8en

copper

have

been

palladium(I1)

reviewed

formed

in place was

through

The

an

of

said

further and

unusual

was

bridge

the

iridazole

to be through

as the

ti and (1‘-for the product

formation

[LPd,(u-OCOMe)] related

been

have

imidazole

ProPYl

complexes

of

the

was

N,C-bridged

treated

showed

with

interesting

[273].

with permission

of nickel.

(45)

diffraction.

used

and

and

in their nmr spectra

Aubidtntatt

complexes

as

coordination

when This

(45) (Reproduced

The

was

[272].

anti-isomer

(46)

behaviour

IPMI*=N'-O]-

for the syn-isomer

the

2-ethylpyridine dynamic

such

quinquidentate

the bridging

derived

species

a

donor

and

ligrndr

palladium

[274].

a complex

from 12711)

The

bound

with

direthylglyoxime

preparation at

the oxire

of

aIT)

nitrogen

and was atoms

34

and

could

also

were obtained

be

coordinated

with

(48) 12761.

inside

the racrocycle

[275].

Similar

results

-

-

(471 A

quantum

(48) study

chemical

[(M(RC{-NO)C(-NOH)R'),),1 consideration

(R.R' = H,

different

interactions

of

types

of

(2771. The complexes

Me

intermolecular or

Et)

packing

[ML,],

undertaken

was

and

interactions

the

in

taking

possibility

(49). were also prepared

into

of

M-O

[SS].

(49) Complexes their

[ML,],

structure

[278].

have

nitrogen

in

this

atom

The

nitrogen ligand

mode of binding

in

with

was

through

Complexes

(58)

atom

determined:

reacted

case

[ZSO].

prepared;

pyridyl

been

[Pd(MeCN)&lz]

Binding

been

the deprotonated 12781. Stability

seem to be involved palladiur(LI)

(HL = (88)) were reported:

but

phenolic

there oxygen

Is little and

constants

for the complexes

again

structures

the

PhCB,N-C(Me)C(R)-NOH.

of

coordination

indication

the oxire

the the was

deprotonated syn-oxiae. through

of (81) with not

specified

HL. to give oxiae

(SZ), the

were

and

with

oxire

of

nitrogen

[PdLZ].

the

irine

platinum

nitrogen

and

have the

[281].

(g4) was used

for the deterrination

was not specified

of palladiur(II)

[282]. The complexes

[W(TP)P]

and

but the [M(CPT),]

35

M=Pd

or

Pt:

TPH = (551,

suggested

that TP was bonded

not clear

where

was

bound

structure.

they

through

CPTH

through

believed the

been

the urea oxygen

deprotonation

amide

This seems unlikely

have

= (56))

carbonyl

the

in view of earlier

authors

and the NH group

to have

and

The

prepared.

occurred)

NH

group

data

and in

(it was

that

a

(56)

polymeric

[265.283].

(50)

bH (52)

ON OH

HO (54)

An X-ray from

diffraction

[Pd2(PPrl)&l.]

study

of

and NaCN021

(57).

[Pd4(N0z)41u-ONO)+ [PPrejrJ. in methanol,

indicated

prepared

Pd-0-N(O)-Pd

bridges

12841. 1.6.2.7

Bidcntatc

and

The preparation 2-aminophenol described

or

complexes

of

ruftidentate

Complex has

oxygen

characterisation

2-aminoethanol;

f285].

HO,CCHtN(CHZCOOH),

and

been

RR'NCHrCHzNRzR=

nitrogen

of

{PtLL']

HLL' = HOOCCOOH formation

between

investigated (R = RZ = H

or

[286]. l

donor

ligands

(L = 1.2-diaminobensene. HO&CH&O,H)

has

palladium(I1) Palladium

R' = R= = CH,COOH;

and

been and

platfnum

R = R' = H.

36 R=

t

Rs

R

= ctiZcoofi;

ligand

Metal

but

12871. The

thermal

by

DTA

decomposition

uncoordinated

carboxyl groups.

HCl

loss

it

carboxylate also

became

tetradentate

this

Equilibrium

of

ligand gave

constants

nitrogen

observed

process

but

the

structures

of

binding

halo

halides

investigated loss of was

the initial loss was through

also

but after

deprotonated

(HOOCCH,)zNCH(CH,)CH2N(CHtCOOIf)~

complexes

analogous

to those the

for

determined

were

of

in

absence

the

(H&L = (55)) was

(HOOCCH~)~NCHpCH,N(CR~COOH)CH~CH~N(CH~COOH)CH~CH~N(CH~COOH)~ determined

characterised.

was initially N,N-coordinated

with

[288]. Complexes

groups

investigated;

[289].

first

been

In [Pd(&L)Cl,].2HCl.2Hz0

of COz. &L

of water and subsequently

in

of [Pd(H+L)] The

have

through

forred

were

N.&chelates

therrogravimetry.

and

= Rs = CHpCOOH)

exclusively

was

binding

complexes

= Rz

R’

s

the

species

formed

of edta&

reactions with

were

were

not

Pd*+

of were

elucidated

[2901.

(57) (Reproduced with permission

from [284])

,,,,.t N (CH2COOH I2 ck

N(CH2COOH)2

(58) The [ZSl].

reaction Extraction

of

the

ferrocene

equilibria

derivative,

of palladium

by

(5s).

[292].

showed

that

the

extracted

species

(50)

trichloromethane from

7-~i-ethenyl-3,3,5,5-tetraaethylhexyl)-8-quinolinol solutions

with

was

a

(51)

solutions

aqueous

simple

gave

of

chloride

chelate.

CHLt I.

complexes

Palladium(I1) ethanones as

and

propanones

have

been

CPdLLX,l.

(62).

.[PdLC12],

2-(substituted

of prepared

t-1

l

and

and

pyridyl)-1-phenyl

characterfsed. (64).

[PdLZ].

Species

were

such

described

c293.2941.

A range

of O,N-chelating

deprotonated

phenolic

provided

the

by

molecular

OH group

ligands

were

donors

(bs)

complexes

indeed

and

have

been

[ZSS]

and

An X-ray

[297].

phase

reported.

was

found,

incommensurate Further

formed.

involving N=N

A

on

for the phase of

on

the

alumina

were

as

complexes only

the

and

showed

that

complexes

stacked

structures

(M = Ni.

Cu

a commensurate

of 1:l and 3:2 stoicheiometry pH

(67)

alternately

of

were

to make

there

of

or

Pd)

monoclinic was

also

an

[ZSS].

[299.390].

of the pyridine

Although

study

and nickel

examples hoped

of the adduct

between

complex

atom and a

4-(2-pyridylazo)-1.3-dihydroxybenzene.

Complexes

depending

It was

such

study

metal

copper

Interesting

[ZSS].

species

further

the palladium

modulated

coordination

w-bond.

supported

but

complexes

have been studied. were

For

studied.

interactions

a-bis(u-methyl-2-hydroxybenzaldiminato) has been

an imine nitrogen

(66)

diffraction

a-a-molecular

acceptors

involving

chelated

of

1,3,5_trinitrobenzene. there

ligands

structure useful

Soviet

nitrogen proposed

catalyst8

authors

l&L.

with palladiua(II) proposed

atom, deprotonated was

for

(ea)*

unlikely. nitrobenzene

a species OH and the

these

Specie8

hydrogenation

38

[301.302].

Palladium

complexes

3-sulpho-5-nitro-2,2', were not metal

simple

bound

of

5-sulpho-2.2' .4'-trihydroxyazobenzene

4'-trihydroxyazobenzene

1:l species.

and the

have

authors

did

been not

reported,

know

which

and

but

they

atoms

were

[303].

OH

(69) could peracid

be synthesised

oxidation

three 1:l complexes entirely

On

of palladium(I1)

the

basis

of

RC(=O)C(*iWPh)C=O)R', an

Y,0-chelate

represented (M = Pd

or

Pt;

spectroscopic

characterised

the reaction

In

the or

[308].

13093.

ligand

of

the product was

with

(71) with formed

conducted

PdC12

depending

[305].

or by

pafladium(I1)

(72)

almost

was

used

[306]. 'H

clearly

R = Ph

data

of the

mar

IR

and

exists as the hydrazone

was

13071.

reaction

In the reaction

could be identified.

on the pH at which

in analysis

from

of (70) [304].

formed

and

spectroscopic

tautorer.

was

equally

clearly

(chroran-3-alkanoyl)hydrazone Me). The

the

series

Palladium(I1)

structures of

(78)

complexes,

complexes

of

data

In the complex

proposed

(74). were (75)

inaccurately

complexes

were

(X = 0

HL. [Pdrp I

CMLClzl from IR

isolated or

S)

and were

39

coordinated (76)

through

were

the

carboxylate

and

quinazollne-(3H)-4-ones, (77a) and

aride

(W),

N-H

177b) the amino nitrogen

atom

participated,

XT

bound

functions, (3101.

of stolcheiometry

(77d) the NH group was said to be nitrogen

and

whilst

Numerous

of

corplexes

of

atom was metal bonded whilst involved. with

In (we)

(TWr)

and

in

(77~)

In and

and (771) the pyridyl

(ni)

-Q-N=dW\ 2 O\ P

0

those

[PdLzClz] were prepared.

formed [311].

R

whilst

2

I

0 0

(ml

NMe2

o.O-chelates

wre

40

NHCOR COOH (75) lR'

1.6.2,8

,The of

the

ligands presence [312].

Bidentatc

reaction ligand

to

and

the

of

Ag+.

oxygen

of form

chelating

chelate The

(77a)

NHZ

Me

(77bl

NH2

Ph

(77c)

NHPh

Me

0Td)

NHPh

Ph

(WeI

2-pyridyl

Me

<77f)

2-pyridyl

size.

W&I

OR

(77b)

OH

Ph

‘Pm*

was

depended

example. (79)

lfgands

[Pttcod)X,]

complexes

intermediate.

MeOwPPh2

donor

with

For

Ph Me

phosphorus

PhzP(CI&)OMe

R+

(78)

reacted

was

on

studied. the

nature

converted

readily

The

with

of

carbon

[email protected]

MeO,-,,-PPh;

J “C-N p+,-+h2p -= p4&p---4-PPh*



“Cl

the

other

to (I#)) in the

*g+ -7

M0-4~~~2,

tendency

+ Pt R-co ‘Cl

so

monoxide

41

X.6-2.9

Bidcntete

o.xy#cn

[Pt(PPh,),(n'-PhNO)] characterised

by

carbon

X-ray

ligands

donor

reacted

MeOOCCrCCOOMe

with

diffraction

to

give

(31).

[3133.

(81) 1.6.2.10 A

Unidcntate

range

of

of

formula

species prepared

complexes

or

data

coordinated.

and

Reliable

two

ligands

proposed

all

<

ENO,]-

was

the

the rate

the

favoured

to

have

Treatment

the

was

coordinated

carbon-carbon

Polarographic electron The and

at

double

process complexes

characterised:

1

and the

hydroxyl

with

the

ion

complex

studied. leaving

or

The

the of

other

in was

high

group

in

but

low

was

Ph) The

was order

ammonia

species

MepS

formed

but by

with

little reaction

was no

prepared

gave

reaction

when

the

starting

all

cases

In

apparent

proved

activity L.

with

formed.

from

complexes

antifungal

4-thiahepta-1,8-diene.

X = Cl.

sulphur bond8

also

propanone.

clr-[Pt(NHS )*L,]

cis-Isomer.

by

first

IR metal

solution

displacement

but

Me

R = H, aqueous

with

was

were

[318].

in

for

basic

nucleophile

Further

halide,

antimicrobial

polymer

With

a

the

[clo,]).

diaquated

were

were

[314].

displaced

incoming

< I-.

was

group

that

or

IPt(MezS)C13

In

octahedral

[M(RS),]

atoms

CBltNl

were

the

[NON]

polymeric

[315.318].

meant

for

< [SCN]-

[Pt(NHo)2X,]

bridged

to be

an

and

sulphur

nucleophiles

ligand

KBr

moderate of

other

(L = {82). and

trans-[Pt(NH,)2(OH)L]+ sulphur

of

< Br-

leaving

[PdLzClp]

appeared

involving

Me,S

[Y] =

I; the

I(Pt(MerS)Clr)rl,

nucleophile

Trans-[PtL2Brz] trans-

or

only

published

constants

< ENS]-

when

of been

mechanism

of

Br

that

complexes

Reactions

with

occurred

X = Cl.

including

(HRS)

[Pd(HRS),][Y]Z.2HZ0

cfs-[Pt(MeZS),(NH,),]'+

in A

trans-effect

cl-

the

have

[317].

ammonia,

Pt,

syntheses

stages.

ligands

N-methylpiperidine-4-thiol

of

implied

[Pt(Me2S),C1][BPd] amaine

donor

[M(HRS)X2].nH~O.

(M = Pd

spectroscopic

sulphur

[319]. initially

X = [NO8]_

the

interaction

A

material. sulphide

with

the

[320.321].

reduction

of

[Pt(NH,),(tu)Cl]Cl

was

shown

to

be

a

two

[322]. [M(PPh,),Lp] they

appeared

(M = Pd to

or

involve

Pt.

HL = PhNHCS&t)

monodentate

were

S-coordination

prepared of

the

42 ligand

[323].

Complexes were

cis-[Pt(DMTC)ZClz],

to

inhibit

Co(II)

calcium(I1) little

in

effect.

inhibited

the

rrans-complex

of

ff.N-dimethyl-0-ethylthiocarbamate

shown

to increase

accumulation

rat

liver

The

cis-isomer

ATPase

and

activity

The

oxygen

release

corresponding

reduced

of

had a lesser effect

induce

to

nitochondria. also

nitochondrial

the

of

accumulated

crane-complex

transrembrane

subaitochondrial

(BMTC).

consumption,

had

potential

particles:

and

again

the

[324].

Ph

(82) When

trans-[(C,P,)M(PR,),(SzCfRq)3CClO*] EtzPh Bu).

was

trane-[(C,FS)M(PR,),(OCIO,)I

or

R = Bu.

The

related

RI = Cy bipy

or

was formed

R = Ph,

complexes

R' = Et

were

also

trans-[(C,Ps)Pt(Pgt,),olCCIO~]

was

treated

with

CR$PCS, I- t

(M = Pd. R3 = R; = EtS. Buo or or

Cy;

M = Pt.

prepared

and

established

R = R' = Et

or

_the structure

by

X-ray

of

diffraction

[325]. Reaction presence

of

ligands

were

PdClz

in

of

l-methyl

HCl

gave

S-bonded

1.6.2.11 XPES

Sidcntate

and

multidentate

were

indicated Small

that

degree

complex Reaction

and of

diffraction

of

the

metal

to

mulphur

were

ligand

Se) was

in

back

donation

adopted

[{Pt(PPhs)(u-SMe))t]

with

a

NO

C3281. S

A

p

L

L

the

prepared

(E = S)

the

All

from

by

X-ray

to the palladium

1741.

ligands

[(PhsP)zPt(p-S),Pt(PPha)zl.

o-coordinated

t&Al

PdClt

C{Ptz(~-S)zL4)2~gjIBPh431.

[{Pt(PPh,)(m-We)),]

L’

donor

for

and

phosphines

(E = S or coordinated

reported

[(PhsP)nPt(u-S)(u-SMe)Pt(PPhs)z]

with

characterised

was

atom was directly

and

(Yimt)

[Pd(Mimt)4]Clz .2&O.

complex

[Pd(ECl,)Cl,)

solution

The sulphur

data

orange-red

[326]*

non-aqueous

diffraction.

inidazoline-2(3H)-thione

an

to

[327].

square

gave

platinum Both

planar

(84).

These with

this

only type

geometry,

identified

by

a of


43

(84) (Reproduced For reasons

Progressive

with permission

of clarity the phenyl

heating

in an inert atmosphere

lC

from 350-550

gave the polymer

from [328])

rings have not been shown.

of

[Pd(retH)(NHs)z]CPdCi~]

in air or

(8s) 13291.

Me

(8s) The reaction (W = Pd

or

Pt).

The

c3301. The structure

X-ray S-methyl the

diffractlou groups

were

trifluoroaethyl

conformation

acid, HL, with

of 2-hydroxydithiobenxoic

[332].

mode

of

binding

of

the

of (8S) was determined

data

for

syn and

(87) and

S-rethyl

This groups

was

not

entirely

by X-ray dlffractlon

(88) have

lay on the opposite

aubstituents. The

llgand

[HCl, I'- gave

in

to were

the also

clear

In (8~) the

side of the chelate

(66)

]

[331].

been reported.

corresponds

I&

rain

ring to solution

q utually

syn

44

13331. Tetraalkyl high density

one-dimensional of

ammonium

optical

salts

recording

materials

[Pt(dept),l*-

of (89) have

media

with

[334].

been used

a pscudo(SN),

bundle

and bis(benzildioxire)copper

Epr measurements

in the solid

(CuN,} units alternated

state

53

x

F PiCIz

S/

Y

f Me

synthesis

described

of

mixed

metal

The

related

[336].

[337].

([S,C,O,]z-)

zig-zag and

Bimetallic

bridges

complexes chains,

of

(3383.

revealed

dithiooxalate polymers,

one-dimensional

formula

The A atoms

the manganese

atoms

and

k

(91)

has

Ptcl 2

S’ I Me

t-1

or Pt) have been prepared. platinum

{PtS/)

Ii t-1

prepared

that

(88)

R

been

1:l complex

Me

(87)

The

a

(IIldept = (90)).

revealed

F

t s\

structure

of

of novel

13351.

Me

rr,

synthesis

was prepared

and in solution

in the stack

in the production

In a designed

X-ray

(92)

and

such

(93)

compounds

diffraction

formed

a stack

bridged

the

data

coordinated

also

(A = Cu,

Ni.

nickel

(S8), with

by

Pd and

extended

to four sulphur

coordinated

been

dithlooxalate

for the copper,

isostructural,

stacks,

as

have

with

[~n(SpC10t),(Hz0)~].4.5H~0

that they were

(II) atoms

complexes

six

atoms oxygen

(94) (Reproduced Partial

view down the b-axis

chains.

eaphasising

Kinetic diselenate) [mnt]+using

data

for

complexes

+

Interest

reaction

determined

of phase

spectrophotometric

[cuL,]z-

the columnar

have been

a reversed

ion pair

-

and

generated

platinur(I1)

technique.

This

of [Pd(ant)z]2-

+

by the A!& fragments.

has

procedure

been was

established used

and [Pt(mnt)z]z-

for

Ar

has =

(15) continued.

The

2-. 3- or 4-Cl&&) [M(!$CNEt,),]

13411. He I and He II PBS of

the

13401.

IPdLL']'-

complexes

(M = Co, Ni. Pd or Pt; HL = ArzNCSzH. and characterised

[338])

(L = [nnt], L' = isomaleonitrile (15) [33BJ. Liquid chromatographic separation of

[CULL']*-

in dithiocarbamate

from

. . .A-(SzC202)-Mn(HzO)B-(O~C~S~)...

stucture

palladium(I1)

determination

[PdL;]

with permission

of stacked

species

[ML,]

were prepared (M = Zn. Ni, Pd

or Pt) were criteria

reported.

and

The assignment

considerations

OP

based levels could be clearly on the chrorophore

capability

complexes

[Pd(S,CNR,),J

studied

by

X-ray

Bu,

diffraction,

IR

13431. AS* values determined

experimental solvation

data

Complexes according for

to

The drug an

reaction

(16)

human

in

support

Na2[PdClI]

has

Reaction

initially formed

was

of

(M = Pd

a

[M(PRp)zC1,] [M(acac),]

or

The and

thernogravimetric

differences were

complexes

between

largely

of

the

and

and

urine

the

due

to

Infra-red

[Pd(SpP(OEt)Me),J.

[CuL,] studied

for

M = Pt [349].

of further

type

gave

platinum

HPLC

been

assay

described. and then

from

(95)

prepared

of

by

with

be

with

several

RdP

gave

converted

one dithiocarbarate

prepared

was to

R$P = PMezPh

of the complex be

I

[M(&CHNR)(PR,')I]

could

However,

also

[351]. Treatment

be

CM(SrCNHR)z I.

reactants,

could

)*W

of iodine

deprotonation

were

[348].

could

this

on

aqueous

by

or

ligand

to give (a) reaction

(Pt(SrCNRz)((PhtPO)zH}] n = 2 or M = Mn,

of

with n = 3)

(98) 1352.3531.

were

[S,CNR2]-

has

prepared

[( *O-N

complexes

SnCl,

effected

spectra

spectroscopy

sensitive

palladfur(II)

or Et; M = VO. Co. Cu or Ni,

lg5Pt nmr

were

polyethenedithiocarbamate

recover

In the presence

by

with R'NHz/CSz (R = CHMe,

ligands

with dðyl dithiocarbamate

to

with

and

Pt),

gave the mixed species The

[342].

of dithiocarbamato

rapid

bis(dithiocarbanate).

I and in the absence Species

in

prepared

[ML, (M = Pd or Pt, HL = (HOCH,CH~),NCSzH)

[M(SZCHNR),(PR4)l.

lost and subsequently

c3501.

used

dithlocarbamate

[Pt(SnCl,I)(S,CNHR)(PRb)l Yldmel

A simple,

Cs2 + NoOH b

phosphine

routes.

were

and

The

13461. Insoluble

been

MeNH

Mixed

an increase

platinum

theoretically

ultrafiltrate

and their interactions

Pd*+t

solvents.

chronophore

of the perturbations

CP3CHz)

spectroscopic

by exchange

[347]. The species

prepared.

and

to

or

dithiocarbarato

[345].

plasma

into trichloromethane

inert

palladium

predicted

labelled

spin

was first chelated

extracted

Metal

The data indicated

for redox reactions

those

on experimental

13443.

of

cis-platin

overlap.

CHZCHMe,

in non-aqueous

and

effects

to

(R = Pr.

have

and

based

and an estimate

derived.

nickel

from

techniques been

symmetry

identified

of complexation

r-bonding

of the bands was

of

compared of

0-ethylmethyldithiophosphonate with

[Pt(LL),]

signals

over

those

where a

of

related

LL = [S,PR,]-.

very

large

range

complexes,

species

C3541.

[S,P(OR).]of

and

frequencies.

47 Reaction

of

exchange complex

(R = Me

CPt(S2PR2)t]

two distinct

steps

between

(reaction the

of [S,P(OR)t]-

mono

Ph)

and

with

c-

more complex

RAP.

occurred

in

(97). there was fast

The

reaction

with

the

(Scheme 2) [355].

PhMe2P

S2NHCR

\/\C=N / \s/

>

‘R

/\SA

a phosphine.

ligands.

bidentate

was, however,

PhMe2P\ ,S.;_p” PhMe2P

or

(17)). In the interrediate,

PhMep

HP--O R2Nc\s,pt\p_ >,” p\

Ph2 (96)

[Pt(SzPRz)Z]

+

RJP

II_,

[(R,PS,)Pt(R,PSz-S)(PR;)]

(97)

(17)

E(R,PS,)Pt(PRS)z]+

CPttS,P(OR),

It1

+ Rip -

[P(S,P(OR),)(PRi)o]Cs,P(CR)~] (98)

CR R"P\p$ R' 3P/

fiS,P(OR).

Is\p/ \

S'

R'.P\pt/S\ R'P' 0

'O-R

'S'

(98)

Scheme

of [Pt{S,P(OR),},] CPd(dppe)Cltl

of

H*L' = (HSCHz)zSe

or

nmr

[356].

spectroscopy

diffraction fonophore.

'OR

+ (RO)zPS~R

2 Reaction

Treatrent

p//o

study (100).

in

(HSeCHz)zSe. Bidentate

(99)

IMLC121.

(3571. acted

with phosphines

with The

[RL'l_

were

S.S-chelation

was

as

anion

where CPd(dpw)L’l characterised by IR and

gave

complexes

Palladium

[355].

and

established

platinum

exchangers.

by.an

complexes

It was

not

X-ray of

the

entirely

48

how the metals were bound, but an S.S-coordination

clear

likely

mode seemed the most

[358].

e iu 0

S

--

(loo)

t-1 1.6.2.12 Ambidentate

sulphur

Thiocyanate

be

precipitation

could with

controversy

as

phen derivatives was

prepared

linkage

appears

in

dmf

di N-coordinated

state

gave

product

the

[SSO].

reaction

isonerisr

W

the

in as

ligands

in palladium

isolated

complex.

Heating

irradiation ultimately

by

of

preparation

appeared

A

to

cold

isomer be

formation

of

the

(101).

by

complexes

of

complex

ethanol

in ethanol

rrsno-[Pd(PPr,)p(NCS)z]

in the

bromide

long-standing

the J-nitrophen into

the N-coordinated

which

of

[359].

thiocyanate

When

pouring

However,

species,

presence

[Pd(SCN),J

to have been resolved. and

S-bonded

resulting

at

the 60

'C

in the solid thermodynamic

gave

a

stepwise

characterised

by

It seems likely that the first step in the process was the

X-ray diffraction. formation

chloride

isomer was formed.

the di-S-bonded

gave

determined

palladium

to

donor

nitrogen

of a linkage

isomer

13811.

PR,

SCN

I I SCN-Pd-CmN-Pd-PRS I

I SCN

PRs (101) Excitation [Pt(SCN)

,(H,O)]-.

[Pt(SCN)a(H20)2]

of

aqueous However,

via

acidic

[Pt(SCN),]2-

excitation

a chain reaction

in

the

in

ligand

a ligand

field

to metal

of a radical pair 13823.

band

gave

CT band yielded

49

An

cis-[Pd(SNNMez)(AsPh3)C1Zj ligand

was

S-bonded

(2.249( 1) A)

A

formed

reaction

of other

with

1:4 complexes

rates were determined,

tic

The

and

metal

of

the

study of

a range

with

formed

multidentate

chelates

quinoline

and

complexes

of

with

S.N-

or N.O-

showed strong tailing The dependence

of anions

and

Caz+

modified

by synthetic as

several

donor

has been

and

derivatives

ligands

of

the

ligands

2-•ercaptoaniline studied.

complexes

with

Both the

deprotonated

and

thiol

and

range of 8- and E-substituted

derivatives

was

also

investigated.

gave

satisfactory

were

adsorbed

O.O-chelates

and

palladiua(I1)

S,O-coordination

The

results

on

irreversibly

or

[367]. of ATP hydrolysis

through

phospholipids function

by Ca'* and Mti+

sarcoplasmic and other

of

5-sulpho-8-mercaptoqinolinate. lipid modified

short

constants

and

transport

a

very

[364]. Palladiun(I1)

Stability

nitrogen

[366]. A related

of the rates

ATPase,

studied

[MLz]

coordinated

but

of

also prepared.

[Pt(NH,),(tu)Cl]Cl

been

quinoline-Y-oxide

chromatography,

bond was

ligand were

PhSOzNHCSPh.

sulphur

has

simple

structure

but modes of binding were not 13651.

N.N-direthyl-2-mercaptoaniline

amino graups metal

the

N-thionitrosodimethylamine

of this

8-mercapto-1.2,3.4-tetrahydroquinoline,

platinum(I1)

of

palladium-sulphur

complexes

its reactions

1:2 and

1.6.2.13 gidentstc The

that

[363]. A polarographic

as have

1: 1.

demonstrated

to palladium.

number

all S-coordinated reported,

determination

crystallographic

X-ray

reticulum

manufactured

was

shown

to

SR more than it did before modification

activated membrane

triglycerides

structure.

triglyceride

(102).

(SR)

inhibit

was

Platinum

the

ATPase

of

[368].

(102) The

ligands

formed similar structure of

the

H~NCH&HZCH(SH)CH&HzNHz

binuclear

related

techniques.

structure

diffraction.

species.

Despite

palladium-sulphur The

complexes

of the complexes

The

(101)

H~NCHzCHpCH(OH)CH~CH~NRz

such as [(103)][ClO,],

being maintained

a somewhat

II

was

in solution

determined

disordered

bonds were abnormally of

and

structure

short

and

nitrogen

atoms

(M = Pd or Pt), the [SSS]. The structure

by

X-ray

it was

diffraction

clear

that

the

13701.

[Pt{HtN(CHz),S(=O)Me)Clz]

sulphur

both

of

was the

determined auino

by

sulphoxide

X-ray were

platinum

coordinated

conformation

and

the

six-membered

chelate

ring

adopted

Me2N,

S,

CI

a

chair

[371].

*

Pd Pcf’

2

(104)

(103)

Further HL. such amino

thioamide

as

complexes

[Pt(HL)ClzJ.

group.

In

trsns-couplex

[PtLZ]

[372].

have been prepared.

(106) was the

coordinated

amino

Palladium

group

was

analogues

said

to be

were

However.

other

on the basis of IR and DV spectroscopic

proposed

structures

of. elOe),

via the thiocarbonyl

tautomers

workers

In derivatives

and the

deprotonated

also

in

synthesised

involving

thiol

evidence

a

[373].

and

thiolate

13743.

(106) The

electronic

(M=Ni

or

spectra

Pd;

4-phenylthiosericarbazfde) bisthiosericarbazone)], were The

investigated

structures

conclusively

stoicheiometry Complexes were

ammonium ligand.

of

after

of dithiocarbazic Ln

(108) 9 whilst through coordinated could

[Pt(PhL-H)(PhL)Cl].

be

isolated.

[Pt(PhL-H)*]

antibacterial

the

properties

to

H2NNHCS,Me

ligands

thiocarbonyl In

and

or

[Pt(glyoxal

complexes

attempt

[Pt(PhL)~ClzJ,

the

[&Cl*]

of

12681.

(1W)

establish

was their

complexes

of

13771.

acid esters, in

13753.

Diphenylthiocarbazone

[PtLIJClt

and

(HL' = H,NC(-S)NHN=C(CH,)COOH)

palladium(I1) little

13763.

salts,

rrans-isomers

limited)

[PdLz] were also studied

prepared.

recorded

[PtL'z]

the

[MLClz]

1-phenylthiosericarbazide

been

and

(rather

behaviour

unfortunately

investigated,

complexes

the

have (106),

for their

electrochemical

(PhL)

of

L = thiosericarbazide,

the

species

[Pt(PhL-2Hjn]

were PhL

(L) and PhNHNHCS*Me coordinated

acted

group.

as

the

unidentate ci*-

Both

[Pt(L-H)l]. XPBS

a

as

and

[Pt(L-2Rjp].

indicated

that

the

51 platinum

atom

oxidised. existed

was

still

Str,uctures

in the

such

as

as a cis/trans-mixture

+2

oxidation were

(109)

state,

the

proposed

for

in slow equilibrium

ligand

having

[Pt(L-H)t].

in solution

been which

[378].

I

NH;

(108) Milligram

quantities

2-rercaptobenzthlazole Was

Iloo)

[ML,],

which

of

(HL)

in

precedent

platinur(II) chlorinated suggests

be

extracted

The an

w

I-I

species

using

extracted

S.lv-chelate

(110). formed

this could be used for determination

0

be

solvents.

should

2-Thio-4-oxo-1.2.3.4-tetrahydroqulnazoline, palladium(I1);

could

13791.

a 1:l complex

of the ligand

iith

[380).

s H

0

010) Reaction On

reaction

[PdLCl]. structure [381].

of

2-mercaptoanillne

with

[Pd(PhCN),Cl,]

Although appeared

the

data

to be

with this

provided

thlophene-2-carbaldehyde gave was

(112) in which

a not

red

complex

definitive.

the thlazoline

of

gave

(111).

stoichei~retry

the

lO8t

likely

ring had been opened

/ \ rQ

52

a

(111) A

range

the NMe2 group

were metal

effort

[Pd(ll4),] evidence

was

data suggested

at

proper

safd



PCKI

s’ (3321

structural

such

as

that both the sulphur

it seeas

complexes

to involve

was presented

and

bound.

Palladium(I1)

I

I

of' N-alkylphenothiaxines

CPdLC1zI.

IR spectroscopic

[382].

polymeric

little

complexes,

of

were prepared.

I

r;i

of

likely (7)

that the complexes

were

also

characterisation

N.S-coordination

(113)

atom and

prepared,

[SO].

The

of the thiourea.

are with

complex

but

little

(3831.

S

(1131 Several prepared

of

complexes

the

Structure

obtained.

whilst

(116) was proposed

(117).

techniques.

related

Both

(lb). atoms

distance

bridged by an ethanoate

ligand.

or in

group

[MS).

[Pd(HL)X]

the

donor

of (115)

characterfsed

was adopted

square

was the longest

planar

recorded

[CypPCSz]-

acted

have

unit

been

CPdLl,

In

was

t&S.

(R = C&C&NNHC&C&

by

X-ray

)

diffraction

coordination

and

the

(3.88 b) for such atoms

[385].

(118)

(115) 1.6.2.14 Bidcntatc

(HzL).

CHzCHzNHCRzCH2).

for the derivative

to

palladium

palladium-palladium

tetradentate tCH2 1,

(R = CHzCH(CH,).

StMz-coordination (3841.

(114)

and

as

multidentate

a P.S-chelate

sulphur

phosphorus

in

complexes

the

donor

EPdLt]

1 igandr

and

fPtLz I,

53

both

of which

study

were

shown

trans-geometry

to possess

by

an X-ray

diffraction

[386].

ad$-J am

a(2)

(117) (Reproduced

The thiophene were

said

limlted

to

act

[387].

substituted as

React&on

a tetrawer.

cis-[PtLIClz]

=s

trsnr-geometry.

of

in

(119),

of

(118)

from 13853)

(R = Ii or Me; R' = Et or Ph)

[PdLCl,];

the

Ph2P(cHz),SPh

a predictable

formed,

Reaction

successively

phosphines.

P.S-chelates

CPd{PhzP(CH,),SPh)Cl,1. n = 2. but

with permission

when

but

with

S.P-chelate. n = 1. With

the

palladium

evidence

[Pd(PhCN)2C1,]

from the ligand an

excess

complex

of

crans-[Pd{PhzP(CH+)zSPh)zCl~]

gave

for which

either

produced with

was

ligand

possessed

Na[BPh,]

gave

[Pd{Ph~P(CH,),SPh-S.P}{PhzP(Ca,),sph-p)Cl][BPhJ

[Pd~PhtP(CH,),SPh-S,P)z][BPh~]z. demonstrated

that

the bound

[Pt(cod)X,]

(X = Cl

or

Br)

In the

phoaphines with

mixed were

PhzPCHZCH2SMe

with

complex.

mutually

complex

[Pt(Ph2PCH&HISMe)Xz],

presence

of an excess of the ligand and Ag[BF4]

gave

of

(120)

"P

and

nmr

cis

spectroscopy

[388]. Reaction

initially

cis-[Pt(Ph,PCHzCH&Me)z]

the formed

of

chelated in

the

[312].

Cl181 Reaction

presented

(1191 with

RNHt

gave

the

derethylated

binuclear

complex,

54

(121).

Demethylation

isonerisation proposed

of

CPd(2-MeS(CsH.)PPhz)z]z+

of the cis-starting

involved

material

also

occurred,

to a rrans-product.

the amine fn nucleophilic

with

The mechanism

attack by an SNz Menschutkin

reaction at the methyl group of the thioether

type

13891.

, 2 RNH2

1.6.2.15

Bidcntatc

Reaction polymer,

of

sulphur

palladium

carbon

donor

chloride

with

[(Pdz(~-SCHzPh)zCiz}n]

However,

cycloretallated

ethanoate and

which

the cyclonetallated at the electron

cleavage on

bridged complex.

bridge

4-MeCsH4CHzSCHzCsH1-4-NOZ

splitting

with

complex,

ligsnds

Me,CSC&Ph

ethanoate

[Pd{S(Cfl,Ph)CMe,),(OCOMe),l.

substitution

by

palladium

with

3

palladium

The

complexes

in

carbon

bond. was

aethanol

(122). This underwent reactions ethanoate

[390]. gave

(123). in which metallation

a

bridged

product

sulphur first

heating

thiol

a

gave

a

the expected Reaction

single

isorer

of of

had taken place only

rich ring [391].

(122)

Selcniua

epr spectra

donor

and

[M{Se(S)CNEt,),l

temperatures

a

the

(122) 1.6.2.16

of

gave

irreversible

[email protected]

ion impact

mass

spectra

of the

selenothiocarbamate

(M = Cu. Ni. Pd or Pt) have been reported. rearrangement

to

{M(Se(S)CNEtz}(Se&NRtz)]

At high and

55

[M{Se(S)CNEt,){S&NEt2)1 and solvent

at a rate determined

occurred.

1.6.2.17 Tellurium Reaction

donor

and represents complex

[Pt(SCN),]*-

other than K,[Pt(SCN),]

1.6.3 Colrplexes viLh amino

biologically

through

considering

them between

for

methods

contacts

Ht[PdCla]

in

hydraxine The

and

In the [Pt(tep)t]z+

psptides

and

important

from [393])

nucleic

Group

15

ligands belonging

acids

bind

molecules

to

atoms.

donor

cation

palladium

the

to these two groups

and

practice

of

is continued.

acids

for

electroless devices

semiconductor

Schottky

16

Group

1.6.3.1 Amino New

scids,

angles

characterised

C3933.

with permission

Bond lengths and selected

most

yielded ttep) determined by X-ray

2-(PhTe)CsHbPPh,

was (1MI. the first example of a structurally

(124a) (Reproduced

platinum

metal

1fgMSdS

with KzCPtSCN)b] structure, The

of

CPt(tep)tlEPt(sCN),l. diffraction

Since

by temperature,

13921.

with

baths

have

silicon

containing

deposition been were amino

of

palladium

developed.

prepared acids,

Pot-

and

example,

by reductive arino

alloy

contacts palladiur

deposition

alcohols,

with

Nalk p4 1

or

13941. structure

diffraction

of

techniques.

cfs-[Pt(py)(HtNCH&GGH)Clz] The

glycine

was

bonded

was through

determined the

NHz

by

X-ray

group.

and

66 there

were

[395]. and

Intermolecular

Complete

platinum

thermolysis amides.

from

white

to yellow,

from

the

coordination

chloride

gave

hydrogen of

[Pt(NH,)3(glyH)]C1z heating

However, purportedly

a mixture

involving

bonds

to

sphere

[SQS].

of cis-

and

carboxylate

yielded

only

associated

the

'C

150

with

Reaction

the of

[N&

gave

]Cl.

a

groups HCl,

colour

displacement [Pd(gly), ]

of glycine with

trans-[Pdz(HzNCH~COCl)zC14]

glyH

change

thionyl

[3QT].

(0)

( b) (124b) Bond

lengths

disordered

and

(Reproduced

angles

involving

alternate labelled

FD

and

analysis

of

PAB ,

for

complexes. be for

used

desorption the

palladium

both

methionine

and

positions S2A,

mass

only

useful

non-ionic

complexes

for C25A

for

been

[293]) (b). The

the sulphur

and

anion

carbon

was atoms

and C26A.

acid

complexes have

from

[Pt(SCN)4]z-

spectroretric

cis-[Pt(amino

CI was

tonic

permission

(a) and

SlA,

CE

species

Desorption

for

with

for drf

techniques anion)Cl,]-

non-ionic 13953. reported

have and

species. Nmr

been

but

FD

spectroscopic

[399].

A

used

of dlpeptide

rather

could data poorly

57

complex

defined

of

polaroaetrically. described

Treatment

of valH

[PdLL']. Reaction KZIPdC1+]

K[PdLC12]

with

four

or

HL = proH.

proH;

characterised

by

of PdClz

IR spectroscopy with

(L = L-serine

as an O.N-chelate used

converted

L-arginine with

as

molar

the

excess

and

an amino

methyl

reactant

the

The

complexes

acid ester,

(HL = alaH,

mixed

complex

new

[PdL'zC1z]

[PdLg]

initial

complexes

measurements

could be shown

were [401].

to yield

(HL' = S-Me,C-L-cysteine

(HL* = o-benzyl-L-serine).

L

or

acted

When S-diphenylaethyl-L-cysteine

product

was

(125)

which

was

rapidly

HPh2

to

established

ethanoate

(125) crane-[Pd(HL)&lz]

dipeptide

[403].

of

cycloretallation

The

the

in

diffraction

I,

to give

was

of

materials.

Me2

(127)

amino

prepared

acid,

amino

by addition

the

amino

acid

(PhglyH)

with

was

ester

of

the

products

However,

with

was

palladium

CPd(PhglyH)z(OCOMe), 1

(127) 14041.

Et OOC

an

trans-[Pd(NHzCH,COOEt),Clzl

2-phenylglycine

proportions

starting

occurred

of

HL

generally

techniques:

of

mixture the

which

ester were

structure

Reaction a

gave

C(Pd(PhglyH)COCOWe),), ratio

or dipeptide

CPdLz I. by X-ray

N-coordinated

molar

HL'

the

thermograviretric acid derivative

ester), or

of

gave

025)

HCl

was

to (126) 14021.

I

of

studied wave

with HCl, NH* and a further equivalent

and L' as an S,N-chelate.

CHPhZ

The

was

a two electron

HL' = valH)

[Pd(HL)(HL*)(NtI,),][PdCl~].

S-ethananidomethyl-L-cysteine) was

a

of this successively

yielded

The reactions [PdL,CIZl

with

reduction

f400].

HL' = glyH, of

palladiun(I1)

A quasi-reversible

depending

and on

the

MezNCH(Ph)COOEt.

58 A

wide

palladium acids the

range

with

on

(for

was the

synthetic

example

active

spectra

was

bipyraaidal

(diastereomer

S-(+)-CF3CH(Ph)OH amino

acid

[406].

anion

species were

gave

was

Reaction

(129)

investigated

all

and

R-

state.

6-10 a)

In

the

or

14051.

of

of

by

frans-[P&

(18)-(20))

t-8)

the

one of achiral

reaction

nmr

of

vis

proceeded

The stereoselectivity determined

mixed

of amino

least

The

S-PhCH(N&)Me

make

many

at

influence

Further

a

of the reaction spectroscopy

(PBu3)2ClZ(~-Cl)t]

(R = H, Me or CHMe,).

(reactions

to

including cases

investigated

with

transition

excess

developed

ligands

(128)).

optically CD

was

and nitrogen

rrsns-[Pt(SR,)IR,S-valDMe)Cl~~ trigonal

techniques

with oxygen

amines

ligands

ligands

of

complexes

in

with

reactions

an

of such

[407].

(12Sm)R=H (12Sb) R = Me (12Sc)R

SOCl,L

= CHMet

MeOH

(129a) ___)

cis-[Pt(NHZCH&OCl)(PBu3)C121

-

cfs-[Pt(NHtCHtCDOMe)(PBuS)C1.]

(18)

CH,COCl (12Sa) -

cls-[Pt{NI12CH,C(=O)OC(=O)Me)]

(19)

(20) Intramolecular palladium(I1) amino

acids

complexes fractional

spectroscopic electrostatic

acid

interactions

been

rotamer was

interactions

studied.

were

In

populations

concluded

ternary

complexes

could

that

influential

in

be

only

of

mixed two

different

calculated

hydrogen

in determining

ligand

from

bonding

nrr and

the conformations

[408].

complexes

hydrazide:

species,

have

It

data.

of the complexes The

ligand-ligand

[Pdl(LH)&l,]XZ

X =

Cl or OH)

[Pd(LH),Cl,]

are shown in reactions

and

(LH = aspartic

were

[PdL2]

prepared

could

also

(21) and (22) [409].

acid

and be

hydrazide

characterised.

isolated;

their

or The

glutaric related

preparations

59

cold. Hz0 + HL ______)

K,[PdCl,]

(21)

HCl. propanone (22)

PdC12 + HL

A

CD

spectroscopic

S-methyl-L-cysteine L-serine in E.

caueed

calf

growth

has

was

nucleoplasm

sone

changes

noted

and

[SlO]. A combination

cells

and

in the cells.

there

with

were

polymer

of Kz [PdC&]

interior

clurping

induced

pronounced

Inside the cells

also

bound

of

filamentous

clumping effects

significant

and

ribosomes

of the on

the

Pcptidcs

An nmr spectroscopic interactions

the

aaide and carboxylate amines

were

amines

containing

the metal

found

ator.

discussed

A kinetic

of

of non covalent

dipeptide

peptide oxygen.

to be

In more

tridentate

Stability

directly

ligand-metal

palladium(l1)

was

with

peptides

was

binding

basiclty.

chain

amine,

of a range of However,

favourable

aide

undertaken.

through

for complexes

to amine

an additional

substituted

and ligand-ligand

complexes

constants

related

aryl rings showed

in detail

methylethyl

study

in tridentate

[Pd(glygly)Cl]

attack

reported

of

complexes

[411].

1.6-3.2

Im

palladium(I1)

cis-Cs[Pd(L-serinato)Cl,j

but no surface

cytoplasm

of

been

elongation

whilst

B.

study

those

interaction

with

conformations

were

[4i2].

study

of

the

glycylglycinate external

hydroxyl

palladium(II) has

been

ion on

promoted

undertaken. #1?10) at

hydrolysis

of methyl

and

proposed

was

The mechanism

the

coordinated

carbonyl

group

c4133. The

effect

biosynthesis inhibition

in of

polyphenylalanine anti-tuwour

of

cis-CPt(glyglyOEt)zCl~l

Walker the

25

14151.

compounds

carcinosarcoma

aminoacylation

were

[PtA,Cll] compared

of

and was

ci=-platln confirmed

t-RNA

(A = peptide in three

and

on to

the ester)

bacteriological

the

protein

arise

from

biosynthesis and

ten

tests.

an of

known

Prophage

60 induction

in E. coli K12

activity

[416].

E* coli

were

platinum

complexes

X.6.3.3

prepared

been

DNA

was

could

be related

nucleic

for

the

in

the

of

of

with

inhibiting protein

four

of

different

strains

bases and nucleotides

and related

palladium(I1) with

compounds

and

defective

to the antibacterial,

has

to DNA

platinua(II)

repair

antineoplastic

systems:

to the

and mutagenic

[421].

using

to produce of

authors activity

stability nitrogen

the interaction

cis-platin in

[422]. A

cfs-platin

and

binding

at

binding

to

active

platinum

soluble

complexes

hydrogen

peroxide

however, that

a

gave

of heavy metals

simple

polarographic

complexes

DNA

redox

of cis-platin

has

been

might

have

been

purfne

nitrogen

bases

catalysts

the

cytosine

this activity. be

involved

This

in

the

[424].

heterocycles

inidaxole-like

at 40 'C

active

(especially

reaction

pKa

purine

reacted

were

lacking

against

5'-aononucleotides

complexes which

species

constants

at a pyridine-like

nucleosides

N(7)

of cis-platin

determination

Trans-platin,

to

of

However. and

neoplasm binding

protein

with Schiff

Binding

of therapeutically

bases

chemotherapeutic

binding

with

leucine

the

has been used to study

decomposition

derivative).

variety

the

[423].

Derivatives

Plots

binding

especially

platinum

with

suggested

of

metals

bacterial

spectroscopy

for

of

nuclcosidcs

[419,420].

using

nucleotides.

developed

and

of the complexes

Raman

assay

treatment

of the platinum

studied

properties

with

acids

discussed

results

by

[418] . The

reviewed been

derivatives

[417].

Nucleic

Complexation

has

(X) was found to correlate

Platinum

for

established.

atom, fell

purine bearing

The

binding

a

single

nitrogen

6-0x0

group

was

for

N(3) site

straight

atoms

to a

points

or at a pyriridine

on

N(7) a

{Pd(dien))=+

was still

line.

stronger better

14251. The products were

separated

of reaction

between

chroratographically.

N(7) bound adducts

9-•ethyladenine. The

as well as a diner,

species

(131). and

identified

[Pt(dien)Cl]

included. N(1)

and

[Pt,(dien),(u-9-Me-adenine-N(l),N(7)}]

61

[426].

complexes.

The

(ARP = St-adenosine cases

was

N(7)

groups

(L = adenosine or

inosine)

the

or

inosine) been

and

and

studied in

ammonia The

[42'7].

have

were

bound

metal

rrans-[Pt(NHJ)t(AWP)z]Cl~ phosphate

IPt(AWP) *Cl21

K[Pt(AWP)Cl~].

monophosphate)

ligands

were

and

their

[428].

species

hydrogen

In all and

CiS-

bonded

to

the

trans-[Pt(NB~)~LC1]Cl

of

cis-[Pt(NHs)ZLC1]C1

IPt(AWP)IIlCl

epectroscopy.

related

the

preparations

described,

and

by FTIR

(L = adenosine.

hydrolysis

constants

cytosine determined

NH I 2

7

8

The

resulting

adducts

or d-guanosine

were

2:l complexes [Pt(en)Cl,) UV

hours or

-8

and

The

thymidine

were

EPd(glygly)X]

with The

predominating

N(l).N(7) the

at

ATP

pH

for

11.9.

adenosine

adenosine

"C

both

5'-AMP.

were

studied

reaction state,

Guanosine

by

with

after

guanosine.

spectroscopy.

and

I:1

of cis-platin.

the

a steady

d-adenosine

ten

cytidine and

5'-AMP

[431]. complexes

With

GWP

ATP

was

both

were

formed

N(1)

and N(7)

similar,

complexes

such as (lS2).

[432].

that in

with

nmr

reactions

and guanosine

demonstrated

Peptide

complexes rings

[SZS]. The

was

by

with

G-25. With d-adenosine

crans-platin

or GWP.

of cis-platin

with

nucleotide

result

bridged

aromatic

of

at N(7)

acid

were

formed.

It

investigated

amino

formed

with

that

reactions

were bound to the metal Mixed

were

HPLC. and

reactions

on Sephadex

at N(7)

complete.

[4301.

the

[Pt(l.B-pn)Cl,]

spectroscopy

guanosine

separated

bound

and

from

Treatment

with

of

the or

glytyr

stabilised of

by

reaction

bound

N(1)

complexes

bound

glyphe

species

gave

mainly

by interactions with

PdClz

of

between

L-proH

gave

On reaction with either purine or pyriridine nucleosides CPdt(pro)z (u-Cl),l. a mixed species [Pd(pro)(Nucl)Cl] was produced. Adenosine and inosine gave N(1)

or

N(7)

adducts.

with

guanosine

binding

at

N(7)

and

cytidine

at

N(3)

determined

by

[asa].

The X-ray

structure diffraction

interaction there

were

coordination the

of

ammine

with

~Pt(RH,)Z(9-ethylguanlne)&lz].3H,0

techniques. O(6).

large

The

angle8

planes. ligandr

Platinum

geometry

about

between

There at

was

also

the a

platinum

was

binding

was

platinum

was

purine

ligand

hydrogen [434].

bond The

at

N(7)

essentially and

between FTIR

the O(6)

with

no

norral

but

platinum and

spectrum

one

of of

62 cia-CPt(NH,)r(5'-GMP)=]Cl~.6H~0

has been recorded

[435].

--iibose

(182) The

of

reactions

cis-[Pt(NH1)2(HzO),]*+

have

guanine

more

each

structures

yielded

formed

[436]. Reaction 50 'c

gave

determined

involved

of

derivatives been

investigated.

than

eight

Guanine.

products,

ail of the available

of KtfPtC14]

with

guanine,

cis-[PtL(HzO)ClZ].2Hz0.

guanine.

The

from IR and 'H nmr spectroscopy,

L,

l-,

7-

separated

nitrogen

of

and thermal

or

by

atoms.

in the presence

structure

with

(133).

the

Q-methyl HPLC.

of

1M HCl

complex

analysis

The

but not O(6) at was

[4373.

(133)

and

cis-[Pt(NHS)ZLC1). c*s-CPt(Nffa)zLzl. 5'-GMP or cls-[Pt(NH3)rLL'] (L. L' = 3'- or

and

characterised.

The

complexes

HINCH2CMezCH1NMez observations

as

Related derivatives to

the

species were relative

also rates

IMP)

were

from

prepared isolated. of

cis-[Pt(NH,)z(HzO)L]

Sore

reactions

prepared

dien

and

Interesting of

these

63 with

nucleosides

K[Pt(GMP)C13]4Hz0,

research

[Pt(GMP)ZC1,].81i,0,

rrsns-EPt(NH9)2(GMP)p

and

cis-

Hydrogen

group.

St-GMP

with

cis-platin

cls-{Pt(NHS)z(GMP)2] reported. which

After

had

previously

previously

to

a

known

the

presence

and

absence

of

that

unsurprisingly. bis(guanosine)

(X = DzO.

Cl,

cysteine

were

The

{Pd(glygly)}

bound

cytidine

cytidine/guanosine However,

PdClf

and

of

N(3)

or

reacted

cytidine

the

with

to give

the

was

it

careful

((IlSS))which found

for

guanosine

was

the

in

the

production of

the

rather

found,

spectra

have X

and

binding

been

on

of

the and

CiS--

complex

studied.

There

‘J( 'J5Pt-H(8))

guanosine site

was

cytidine-guanosine

a ternary

products

were formed,

[Pt(NK,)(S-ethylguanidine)ClX]

of

N(3)

major

species

More

as

with

limited

9-ethylguanidine)

through

mixture

The

on the nmr spectroscopic

nmr

and

trans-influences

and

evidence

compared

'H

reaction

the primary

chelates.

cis-platin

of cysteine

[442].

I, NHa.dnso cis-

No

of

trano-[Pt(NH,)t(9-ethylguanidine)X]

significant

AMP.

in some but

detail.

structure

or for slow rotation

incubations

the presence

adduct

of

the

and

another

The

new species

N(7)-O(6)

of

by

inferred.

were

species

CPt(GMP),IC12

C439.4401.

considerable

as

assignment

derivative

When

[441].

in

was

data

at 80 'C, however.

described

the

chelates.

postulated

tinescale

studied

The

characterised

to the phosphates

heating

been

led to

were

IR spectroscopic

was

[438].

[Pt(GMP),C1]C1.6Rr0,

and cis-[Pt(NR,),(GMP)(HzO)]+

prolonged

investigation corresponds

fror

made

were

]Clp.6Hz0

bonding

not all of the coaplexes of

complexes

platinum

through N(7)

pair

of

at

N(7). the

N(1)

of

are

(4431. With

a

guanosine. guanosine

14441.

(134)

The CiS-

In

or the

reaction

1:2

structure. O(6)

of

trans-platin

the

complexes

In the

disodium

gave

1:l

cis-

the

salt or

ligand

complex

the

of

inosine

was

bound

authors

(IMP)

5'-monophosphate

trans-[Pt(NH9)z(IMPNa,)nC1z]

only

claimed

at

(n

N(7)

binding

in

through

with

= 1 or 2). a

bridged N(7)

and

[4453. The

complexes

[PdL,Cl,]

(L = xanthine.

(135).

theophylline.

theobromine,

in acidic

spectroscopy involve

were

the

potentiate

lethal

[Pt(caffeine),CllJ

chromosome

were

permitting by

N(9)-coordinated

could

be

stabilised

was

through

with

of

cfs-platin

the

The

[450].

chromatography.

or Both

shown

to

cfs-platin

in

platinum

a

Numerous FTIR

were

N(7)-bound

the proportions

by

The species

The structure the

of the

caffeine [448].

due to a redox

reaction,

in

such

species

complexes

there

from

IR

of DNA lesions

study:

spectroscopy

and

products

[Pt(dien)Cl]Ci

of

cis-arrangement

in water

nucleosidea

intidazole ring

and

diffraction in

was

the lesions.

were prepared.

unstable

reaction

effects

due to enhancement past

[446].

N(9)

Caffeine

damaging

to

prepared.

N(l)-

dimers were isolated,

(135)

to

14473.

X-ray

[449].

been

have

N(7)

interaction

[Pt(NH,),(9-rethylxanthine)]Cl

an

by

[Pt(caffeine)(adenosIne)C1,1 5'-monophosphate

of

replication

somewhat

was

via

were

by IR and nmr

palladium

and K[Pt(caffeine)Cl,]

K[Pt(caffeine)Cl,] but

structure

established

was

1,3,8+riaethylxanthine) were established

to

coordination

and

of a process

bis-complex moieties

the

chelate

cells. This was probably

hamster

inhibition

or

structures

coordinated

established

N(7)-O(6)

Chinese

Their

solution.

all

spectroscopy:

(x36),

caffeine,

3,8-dinethylxanthine, prepared

of

xanthosine

implied

was

no

that binding

direct

metal-O(6)

9-methylhypoxanthine, separated

species

as

of the products

by

as

depending

R1 = RZ = R3 = H

(137).

ion

well

as

exchange

W-N(l).N(7)

on pH [451].

(137)

(136) R' = R2 = Rs = Me

Some

further

of

complexes ( I-MeC,

(I-MeUH,

I-methyluracil have

been

cis-[(NHs)2Pt(l-MeC-N(3))(l-MeIJ-N(3))][NO~].2Ii2O

was

I-aethylcytosine

characterised solution slowly

the

by

'H nmr,

l-MeU

released.

(139))

The

and

IR

ligand

Rqran

with

reaction

(pKa-

studies.

0.9)

was

copper

Thus

prepared

spectroscopic

protonated

was

and

and

In acidic

I-IdeUH

described

to

O(4)

was

bound

to the N(3)

of I-MeU and O(2)

of I-MeC.

atom was in a tetragonally The

reactions

sites

of

of l-WeU

and

Epr spectroscopy

elongated

ligand field

l-MeC,

and

indicated

was give

(140).

cis-[((NHs)~Pt~~-1-MeU-N(3),O(4))(u-l-~eC-N(3),O(2)))2Cu][NO~]~.6H~O, Platinum

and

(138))

studied.

copper

that

to

the copper

[452].

cis-[Pt(NHs)z(l-MeU-N(3))(HzO)]+

and

the

55

head-to-tail were

isorer

studied.

of

The

the

of

product

from

(141).

was

cis-IPt~(NH1)4(T-MeU)~~~l~NO~l~.2Hz0. Each

diffraction.

l-MeU

ligand

bridged

two

through N(3) and O(4). with bonding

to silver

from tram-platin

C453.4541.

was also prepared

the

with permission

The

complex

cjs-[Pt(NH3)&lz]

uracils

in drso

to give

liganda,

[Pt(NH9)zLZl. N(3)

HL = dithiouracil) distinguish The

structure

(l-MeT = (143)) platinum

atom

of

The

[456].

have been

has

was

treated

The 5-nitrouracil

tranm-N(3>,SC4>

isolated. from

a range

of 5-substltuted

was N(1) coordinated complexes

Neither

[ML.]

with

the other

(M = Pd

IR spectroscopy binding

and 5-bromo or

by

X-ray

diffraction.

the other NzOz-bound.

Pt.

nor XPES could

[458].

[{cfr-Pt(NHs)2)2(~-1-MeT)z][NO~]z.

established

is N,-coordinated.

with

centre.

and for the 5-fluoro

tranr-NC3J,SC2)

head-to-head been

polymer

by C and 3MeU atoms by U.

an inversion

[Pt(NHs)z(drso)L)+,

bonded

units,

O(2). A related

from (4523)

1MeC atoms are indicated

The copper atom occupies

ligands

X-ray

by

(139)

(140) (Reproduced scheme

direr,

bonded

cis-{Pt(NH,)z]

(133)

In the numbering

head-to-tail

determined

through

Ag+

with

ci=-[(Pt(NHs)z(~-1-MeU-N(3),0(4))}z]*+

structure

One

of

(142). the

two

Both of the platinum

66 atoms

adopted

almost

square

eclipsed

planar

and

tilted

platinum-platinum

tilt

angle

a-pyridone

[45'7].

dimers

(141) Section

of the

coordination towards and

twist

(Reproduced

with

crystal

structure projected

The with steric site

equilibrium

cytidine

have

interactions do

equilibria

not of

5*-monophosphate techniques.

constants been of

the

the

were

[Pd(dien)(HtO)]'+

of

two

other.

coordination

The

conformed

permission

the

relation

to

from

trends

seen

planes of in

the the

[453]

x-axis.

reactions

of

[PdCl.]'-

Intramolecular

substituents

greatly

reactions (CWP)

the

of cis-C(NH9)2Pt(lMeU)Ag]*[NO~]~.2H20

determined.

exocyclic

contribute

each angle

along

for

with

ortho

stability

to

[Pd(dien)Cl]+

studied

by

was

an

with

and

hydrogen to

the

14583.

intermediate.

bonding

cytidine The

cytfdine

spectrophotometry

IPd(en)C121

(C) and

With

kinetics and

and

binding and

cytldine

stopped-flow CMP

initial

67 coordination N(3)-bonded

was

complexes .NlP . . .

phosphate,

Via

. .

hydrogen

rearrangement

to

the

stable

[459]. ,NZP \ \ .

. .

.

\

.

.

(118) (Reproduced Possible

before

wfth permission

bonds between nitrate

the aamine

groups

from [457])

ligands and the surrounding

are indicated. 0

AY

l-IN 0

I

I

Me

[Pt(phen)(en)]*+

formed

a crystalline

complex

with

cytidine

3'-phosphate

characterised

(3'~CMP),

heniprotonated the

platinum(I1)

cleavage

of

fragment.

and

K2[PtClh]

acid

molecule.

to

diffraction

techniques.

bonded pairs which stacked

This

was

an

monophosphate,

he specific

for

end

product

CpG,

the

by the

RNA

of

for anti-turour,

they had good with

its

[Pd(en)Cl,]

activity

(144) gave

L1210 in

and

2,4-dioxopyriridines

tested

(1451;

with

antiviral

and

derivatives

forned

and [Pd(NHs),]'+

complex

starting

range

toxicity species

of

C-syn-G-anti cytidine

reacted

guanine

ribose

conformer

pseudohelical

or

with

cis-platin

complex.

was

an

of

activity

[462]_ Orotic

with

[PdC14]*-.

Very careful

(approxiaately

an N-type

an

conformation important

with

one

addressed

in viva

a

useful

reagents since

to the

[464].

nmr spectroscopic

between

with

In

the

C(3')

CpG cndo.

to

studies and

C-anti-G-anti

with C(2') cndo.

perturbation

conformation

as

rates. This was especially

20:80).

conforration

d(ApTpGpG)

proposed

or cir-[Pt(NHs)Z(HzO),][N09]z

equilibrium

adduct

the

whereas

the

The C-anti-G-anti

leading

to

a

zigzag

[465]. and

cfs-[Pt(NHS)z(H+O),][NO~]z

complex

had good

and polynucleotides.

to react at different

had an S-type

oligonucleotides

cis-platin monomeric

adopted

represented

left-handed The

there

conformations

riboae

was

of complementary

of oligonucleotides

chelate

that

activity.

[4Si]. Reaction

complexes

damage of nucleic acid sequences

give a C-N(3)-G-N(7) indicated

anti-bacterial

[463].

be expected

CpG and d(pCpG)

The

monophosphate

were

this and related

for the preparation

useful for directed

intercalator.

cls-[Pt(NH,)t(HpO)z]*+ and

low renal

a wide

hydrolytic

(145)

derivatives

two "ends" would

the

14601.

[BrPt{dien(CHp),dien}Pt(H,D)IS+

material

form reactive

of

and in mice, and very low nephrotoxicity

vitro

was

were not cleaved

(144)

The

3'-CMP

above and below

dinucleoside

since d(CpG) and other deoxyribonucleotides

In general

against

X-ray

dinucleoside

seemed

Complexes prepared

drug

the

intercalator

by

and formed hydrogen

platinum

d(CpCpApTpGpG) to atom

give, per

in

were each

reacted

case,

oligonucleotide.

a

with single

'H

nrr

spectroscopy Site8

implied

adjacent

OP

500 MHZ.

In

In

predominated

for

temperature

were

nucleotide. complex.

the

two

considerable

digestion

with

adopted

and 5'-d(GpGpCpC)-3' identified

cross-links

similarly The

[470].

products

digested

duplex

d(GpG) with

involved

in this case only the

guanine

of

The

complexes

cis-platin

by

sensitivity. was

towards

RRAase

interferon the

by

reaction

an

OP

regulatory

with

a

very

established

platinum

by endo-and

with

materials

the

the

by

modified

cxo-nuclease platinum(I1)

residues

to form

cross-links

with

d(GpCpGpC)

self-complementary and

~C~PCPWGPG)~,

and

product

oligonucleotide.

suggested

spleen

calf after

digestion

of

the

also

d(GCCGGATCGC).

activity

was

decreased

DNA

lesion chelate

studied

in

the

melting were

may not

The distortion and

this

enzymes

decaaer

a

14721.

double

may

raises The

helix

[473].

interferon

[Pt(dien)Cl]Cl The effect The

induction

three

types

A

of

of

increased

at low binding and

trsns-platin f4743.

all shown

of the products

and

induction

sensitivity

were

destabilisation

by {Pt(dien)}

interferon

revealed

The

chelation

B DNA,

repair

gave

imino protons

duplex.

by

and

By contrast.

or RNAa8e

eight

bent

investigated.

stabilisation

increased

trans-platin

that

the

crans-platin

d(GATCCGGC)

that platinum

in poly(I).poly(C).

degradation.

induction

of

was

The "sandwich"

manifested

been

of cis-platin

of systematically

cfs-platin,

duplex

have

d[(pGpGpCpC)lz

the

cis-platin

of inosine

induction

with

N(7).N(7)-chelated

of guanine

decanucleotide

detection N(7)

interferon

conformer

conformation

arrangerent

phosphodiesterase

distortion

d(TCTCGGTCTC)/d(GAGACCGAGA)

to fix on N(7)

of

This

or a region

N(7)-guanine

S(C(Z')-c&o)

N(7)-guanine-N(7)-guanine

was 30 'C. implying

bonding.

the

at

14711. adduct

induce a large

question

sites

cis-platin

starting

corplenentary

be a "kink"

of

both

of the duplex

in hydrogen

single

example.

reaction

venom

platinum

a

digested

tetraphosphates

From

the

temperature

the

snake

was cis-[Pt(NHs)t(d(GpG))l The

were

to N(7)

of reaction

with

phosphodiesterase.

for

the

R.R-1.2-diaminocyclohexane

14693. Related

deoxyribotetranucleoside were

For

by HPLC.

established

and

spectroscopy an

in

N(7)

[SSS].

5'-d(CpCpGpG)-3'

intrastrand

the

d(ATGG)

intracellular

an

give

by

N(C(3')-endo)

changes

head-to-tail

enzymes.

selectively

of

adopted

of oligonucleotides

and the products

were

to

a

chelated

'II nmr

the

Ap.A.

in flexibility

was thus shown to bind

by

Substantial

[467].

various

cases-

conformations

complex

dG.

of platination

all

residues

sugar

cis-platin

with

adenines

decrease

site(s)

The

platinum

observed

in

investigated

the

internal

reacted

The

were

all

the

was

[46S].

complex

d(ATGG)

conformation.

platinum

guanines

d(ATGG)/cls-platin

The

that

had

more

a high little detailed

reaction

on the

RNAase ratios

resistance effect

on

study

of

depending

on

70

concentration

and

binding

At rb < 0.1,

ratio.

strand caused some deatabilisation

and an observed

by UV and CD spectroscopy, Of

rb

and

a

lower

polynucleotide

reacted with platinum crosslinks platinum

which

occurred

of

on

at

spectra steps.

At

ambient

were

with specific

by

antibodies.

by

CD

regions were unable

to adopt the canonical

data

were

The

complex

suggested

between

investigated.

The kinetics

were studied

by stopped-flow

fixation

of palladium(IE)

interstrand poly(dG) of

crosslinks

adducts

platinated

adduct

For

were

a

and

spectroscopy.

shown to have B

whereas

platinated

and the presence

diaer

helix

to

single

of

and

this

complex

been

has

POlY(C) with

(Pt(dien)}

The complex was shown to dissociate

of

the

cytidine

were

adopted

of CD

14793.

[480]. Cis-platin

Initially

was

to

the

produced

CD spectroscopy

distorted

on

formed

[481]. The nature

changes

studied. a

binding

to react

conformational

it

to

poly(dAdT).poly(dAdT)

of

alone was reluctant the

that

nmr

orange

poly(dG).poly(dC).

implied

==P

regions were

terms

the reaction

by cis-platin

poly(dGmSdC).poly(dGmsdC)

CD two

groups

cis-platin

of

Z conformation

in

methods.

and

and

bases. The hydrogen

binding

[478].

acridine

to N(3)

and poly(dC)

strand,

the

in

of

UV

showed

amino

conditions,

induced by the metal

formed

in

profile

platinum

and

on experimental

interpreted

hairpin helix transition

and high

[4'75,478]. Fixation

hypoxanthine

Unplatinated

depending

helices

interstrand

No separation

changes

melting

the

the

or Z conformations

left-handed

used

minor

bases

in the second melting step [477].

studied

was

poly(I)

cytidine

predorinated,

the

that

induced

changes

poly(dGdC).poly(dGdC)

spectroscopic

only

However,

indicated

to be disrupted

Conformational

reaction

to

free

At high rb values

crosslinks

led

temperatures. spectra

the

strand producing

strand.

to the N(7) site of adjacent

bonds were thought

the

under any of the conditions

poly(I).poly(C)

80 'C nmr

hydrogen bonded

the double

intermolecular

of the strands

to

in '&,. At a higher value

decrease

concentration

bound to the complementary

restabilised

concentration

(Pt(dien)l

coordination

of the double strand which was established

Z-DNA

in of the

conformation

14821. SERS

has

been

used

complexes.

Cia-platin

coordinated

inside

chemotherapy,

the

however,

The conformational different and

was

types

of

differential

to

study

said DNA

to

the

an

platinum pulse

in double

complexes

changes

corresponding

the

with

platinum

with

platinum

were

which

is

inactive

calf thymus DNA

investigated Both

polarography. to

of

in

C483.4841.

stranded

cfs-[Pt(NH,),(cyclobutane-l,l-dicarboxylate)], Induced

"inner"

(Pt(dien)}.

helix.

gave an outer complex changes

DNA

complex,

interaction

give

of

"premelted"

by

spectroscopy

cis-platin

CARBOPLATIN

the

formation

by CD

induced

and

derivative. but

still

71 double

stranded

whilst

kPt(dien)Cl]Cl

Monoclinic the

deterioration 6 A.

The

give

intrastrand

most

probable

[48S]. However, to

crosslinks amounts

of

at

in

thynus

was found

moieties,

and guanine

AG

was

giving

intercalating

agent

tPt(terpy)(SPh)]+, intercalation

reacted

to

to

with

distortion

no

completion

species

was

hetero

adduct

intrastrand

with

varying

then hydrolysed

chromatographically.

homo

between

adduct between

Most

in

of the

platinum

and two

platinum,

adenine

salts on the binding

of cis-platin

[SSQ].

towards

DNA.

with

nucleic

(146).

of

local

This year there has been a new report of a platinum(II) an

crystal

a resolution

cis-(Pt(NH9)t}z+

regions,

platinated

of inorganic

to salmon sperm DNA was studied

in

their data in terms of monodentate

separated

and a bifunctional

DNA,

containing

resulted

beyond

sites,

reacted

in a bifunctional

[488]. The effect

pattern

non-helical

The

the fragments

denatured

in a solution

binding

is that

and

DNA

"ZmPt-cis-platin. and

GO

interpreted

guanine

Calf

Drug

diffraction

interpretation

other workers

N(7)

acid

radiolabel guanine

of the

crosslinks

[487].

of

sethanoic

a loss

stranded

[485].

cfs-platin.

of

single

tRNAphe were sealed

of yeast

products and

yielded

had little effect

crystals

hydrolysis

ligation

Trms-platin

DNA.

and non-intercalated

For

example

acids

externally

I

in

there

complex acting as

the

was

interaction

evidence

bound platinum

of

both

for

reduced

the

[490].

9, -Pt

0

-SPh

I

0

(146) The duplex was were

presence shortening

unaffected.

and

ethidium

effect. that

interpreted

intermediate

of

in

of

bromide

Whilst

the

trsns-platin

terms

long-range

of

a

during duplex was

model

platinum

DNA

DNA

platination

unwinding

effect

considerably

in

which

ethidium

crosslinks.

Whilst

could still make short range crosslinks.

trans-platin

such links

of the substituted

(147). platinum

has

[491]. A new platinum been

bound

prepared. to DNA

and

complex a

the acridine

study would

of

CPK

be able

of

reduced.

cis-platin The

bromide

results blocked

the cis-corplex

does not normally

model8

acridine

suggested

to intercalate

make

orange.

that

with

one or two

72

pairs

base

duplex

This

away.

unwinding

was

to

be

Like

the

case

acridine

in practice

orange

of light, and may therefore

DNA in the presence photoactivated

appeared caused.

scissors to map platinum

itself,

and

some

(147)

extra

could

nick

be able to act as an internal

binding

sites [492].

(147) 1.6.3.4 Cancer Reviews in

this year have addressed

cancer

chemotherapy

with

C5641

chenmthcrapy

[493-5033,

particular

nephrotoxicity

[507,508].

The

considered

[509]

examined and

the

been

for

their

clinical

and

reference

agents

has

the general

emetic

have

and

of

a

focussed

of

platinum

Structure

platinum

tie-platin and

chemotherapeutic complexes

activity

anti-tunour

complexes

[505.506]

platinum

of

range

[SlO].

on

pharmacology

its

nomenclature

potential

pharmacology

others

to

topic of platinum

been

has

relationships

agents

were

reviewed

[511]. Methods

for

Selective

[512].

cfsplatin

in

as

and

hydrogen

sulphite

activator.

*The

cir-platin

and

plasma

cis-platin 15171. of

The

levels

dual

for as

a

and

platinum

assays

and

for

urine

operation

[SlS].

agent

used

after of

to

pulse

oxidative sensitive

containing

the

been

reviewed

for drugs

post-column

reaction

using

dichrorate

kinetics

rate

of

of

cis-platin used of

methodology

inhibitors

and

[513,514].

was described

potassium

was

JM40

developed

developed

hydrolysis

analytical neoplasm

have

the

polarography acidic

A

was

and

monitor

quantitatively

been

in HPLC

CARBOPLATIN

derivatising

was

fluids

[Pt(en)(malonate)].

have

complexes

Differential

development

in body

platinum(II)

to determine

analogues

of

HPLC

electrode

CHIP

system

15161.

cis-platin

convenient

using

sensitive

of

ultrafiltrate

cis-platin.

detector

in

detection

plasma

Trace analysis such

the

in

in

for

as

an

aquation

of

degradation an

biological

tissue

sodium

assay

of

samples

determination

sarples

was

73

described

in relation

and in laboratory

to

Laser microprobe

tubular

intravenously.

No

[519]. The

in black

mice

the

was

tumour

administered injection platinum

achieved tissues

[522j.

earlier

itself A

using

into

human

then

found

and

number

of

to

rats.

very

when

It was

found

cis-platin

was

intraperitoneal several

cultured

anti-tunour

acid

[529].

cis-platin

of

in

vitro.

ppm

of

activity

agent

soft

in

agar:

contrast

to

found to be

in rats were

was thus prevented

rat

the

than

nephrotoxicity

and

the

dog.

and

cis-platin

earlier

synthesis

platinum

investigated.

the

phase

were

species

separated an

cis-platin

and CARBOPLATIN

elucidate that

excretion accumulated

the

differences

whilst of

renal

cis-platin

to a greater

handling

of

on

involve entry

of anti-tumour of

toxicity and

a

a phase

with

in

compared

was

of

studied.

noted.

and

reduced

half

extent

[533].

that

of

of

than tie-platin

was

investigated;

also

been

phase peaks The

the

and

a

two

were

prolonged to

the

pharmokinetics

attributed

of

animals

complexes

in order

compounds. were

CARBOPLATIN. in red blood the

of free and

cis-platin

of

in experimental

two

were

has

secondary

the

both

15311.

initial

nephrotoxicity

levels

reduced

in the nouse.

activity

infusion

recirculation

were

cis-platin

rapid

to

vomiting

[532]. The pharnokinetics

showed

of

binding

cfs-platin

previously

term

and

formation

and

established short

reduce

thiosulphate

dithiocarbamate

nausea

effect

sodium

than

by

of

to

cell

to

acetazolaride

[527,528],

impairment

enterohepatic

existence

shown

effects

after

curves

of

mechanism

fluid:

the nephrotoxic

physiological

glutathione

terminal

of

selenite

[530]. Diethyl

and there was no inhibition

The mechanism

sodium

shown

diuretic

local gastrointestinal

Beneficial

been

the

was

extracellular

have

included

The

toxicity

macromolecules cis-platin

have as

in

renal

the

as an anti-tunour

in

coadministered,

These

[Pt(S,O,),]*-

shown

were

was

[521].

solution

of cis-platin

lower

if

contained

cytotoxic

metal

in adenocarcinoma

analysis.

spectrometry

carcinoma

usually

selenium.

inhibition

total

DNA

liver

in the

cis-platin

heavy

multiple

After

to

be

platinum

the

distribution

platinum

colon

compounds.

diethyldithiocarbamic

An

the

of

activation

more

[520].

have

nephrotoxicity.

1525.5261,

noted,

in humans

[524].

cis-platin

the

neutron

[523]. The metabolites

results

nephrotoxic

more

of platinum

by atomic absorption

from

was

metabolism

had been administered

localisation

has been used in a parenteral

Cells

cis-platin

of a dog which

concentrated

cis-platin

Cis-platin

cis-platin

(LAMMA) was used to detect

prednisolone

as measured

of

subcellular

deterrination

with

of

cells

definite

obtained

evaluation

[518].

mass analysis

renal proximal

that

the

animals

It

similar.

CARBOPLATIN cells

secretion

by

to was the was

[534]. The the

kidney

74 was

improved

pathology tubules

in

administration

deep

doses.

cortex,

probenicid

due

to

hydration

and

to

furosemide

to

a

study

necrosis

appeared

intracellular

administration

of

renal

of proximal

subcapsular

changes

the

In

selective

extended

of tubular

damage

[535].

caused

which

The mechanism

regeneration

Adequate

of

shown that cis-platin

the

increasing of

by

it was

tubules

with

to be disturbance

respiratory

reduced

system.

nephrotoxicity

C5361. Other enhanced

its anti-tuaour

interferon regimen

C538.5391.

for

selective

activity

which

leukaemia

enhance In

was

attempt

degrees

cured

neutral

to

higher

Zajdela

shown

that

levels

in leukaeaic

session

cells

cis-platin

r-ray

at drug L1210

dose,

used

in mice

tumour

mouse

of

was

carcinoma

mice

Step-down

were

heating

had

to

[543]. 180,

sarcoma

temperatures

the

of

a

few

used

in

little

[545]. not

of NMRI mouse

on the ability

highest

cfs-platin,

low

transition

significantly

In a study

[546].

effective

the

used

and

[542]. The encapsulation

of

[544].

did

and

ascites

temperature

of cis-platin

cfs-platin

in rats

a

C5371,

the most

whilst

lecithin-cholesterol)

having

hyperthermia

neocortex

depended

using

treatment and

rectal

the

local

on the developing

the

C was

15401.

hepatoma

and

synergistically

spirogermanium

5-fluorouracil

(egg

cis-platin

It was

efficiency

mytomycfn

in a single

optimise

effect on the cytotoxicity

ATP

with

alone,

liposomes

that

with

combination

included

of the drug on Ehrlich

containing

cis-platin.

mesothelioma

Ascitic

ineffective

the activity

an

human

with

These

A combination

against

were

in

liposomes

activity.

[541]. By combining

in mice

cis-platin

coadninisteretl

xenografted

and aethotrexate levels

when

compounds,

embryos

of the drug

alter

intracellular

of the effect

of cis-platin

or fetuses

to pass

the teratogenic

the placental

barrier

15471. Guinea

pigs

intravenous

were

administration

of [lssmPt] was greater animals.

rodent

animals

and

evaluate

canine

the

physiological osmotic

models

between

blood-brain

at

various

cis-platin.

of the pretreated excretion

of the osmotic

intracarotid

of the

labelled

damage

neuropathological

procedure,

modification

that urinary

due to kidney

relationship and

of [lssrPt]

cis-platin

in the tissues

It was concluded

pretreated

with

pretreated

drug

effects

of

administration barrier

than of the control

[548]. Cis-platin blood-brain

with

the

was decreased

fn

was administered

to

barrier in drug. of

resultant

before

The concentration

of platinum

concentration

times

modification

the

brain

Even

without

cio-platin severe

and

to the the

produced

neurotoxicity

(5491. Guinea

pigs treated

in the basal

turn

with

cis-platin

of the cochlea,

showed a 60-70 % outer hair cell loss

and a decrease

in the auditory

brain

stem

response

waveform

the' outer tubular

hair

necrosis

Cis-platin type diploid were

in

adducts,

was

strain. The

was shown strain

rather

deficient

The overall and

(D7 rad 3).

dimers

or

similar

the

diploid

strand

breaks.

to

be

52),

hypersensitive blocked

discussed

in the

in terms

of

in

vivo

protein

was

examined.

synthesis

was

[553].

renal

induced

synthesis.

leukaenia

of

than

cell

death

and

proteins thiourea histones

This

cells

extent

of

and

rat liver

the

overall

50 f.

Protein

was unaffected,

resulted

was shown studies

but normal

to the same extent

from

a

lower

binding

and

were,

non-hi&one

as of

rats

conducted. were

The other

less

C22LR

2-mercaptoethanol with

as

active

dogs

of

corplexes cfs-platin

against

the

[SS].

proteins

considerable

and

as active

however,

after

on the availability

mice.

to

to cis- or rrans-platin

and the action

treated

in rat tissues

to depend in

were

(148).

cross-linked

Ii1 were

the

inhibited

L1210 and osteosarcoma

to DNA,

nitochondrial

of

to metallothionein

They

chrorosoral

or

to

cis-platin.

cells.

types

hepatoma was

on

Prom regenerating

[552].

nuclei or intact ReLa cells exposed complexes

both

synthesis

and TNO-6.

step

cis-platin

inhibited

Preclinical

toxicity

Cross-linking

by

cfs-platin

In

of cis-platin

CARBOPLATIN

tumours.

blocked

as was

of DNA double

repair

of

of Zajdela

protein

protein

hemopoietic

containing

cis-platin,

in hepatocytes

of cfs- or rrans-platin

groups

non-histone

to

administered

synthesis

to tuaour mitochondria

platfnum

phosphate

strain

hepatoma

the injection

mouse

a

pyriridine

in the mitochondria

lower

in

The diploid

to

The in vivo binding

had

dissolved

solution.

overall. cellular

against

in the wild

the genotoxicity

UV-induced

protein

cis-platin.

was

and

(551).

Zajdela

-SH

medullary

and mutagenic

the cytotoxicity

cfs-platin

kanamycin

excise

ability

rat liver mitochondrial

of

the

with

cortical

[550].

were noted

recorbinagenic

Both

combined

marked

aqueous

were

cfs-platin

nephritis

was

and

than in simple

effect

cellular

if

cis-platin SO-100 %

an

cellular

synthesis

to

to be both

reduced

(rad 52/rad

genotoxicity

rose

D7 of yeast.

shown

results

loss

and interstitial

considerably

buffer

When

and amplitude. cell

DNA

could

15543.

Calf

isolated

was studied.

numbers

of both

in

of

be reversed thyaus

cis- or frans-platin

Both

chromosomal and/or

nucleosomes

at low binding

76 ratios. was

A

change

observed

behaviour

in

after

of

the

new

and/or

KB

their

and

of

negative

bearing

assay

polyploid one

was

negative

that

required

in

all

inhibition

to

cases

of

it

mitosis

be

were

block

Thermal

melting

cis-platin.

and

prepared

in

Forty

assayed

a

new

complexes

a

were

for

stable

P388

tumours

evaluated

L1210.

true

search

water

against

leukaemia

complexes

An

positive,

induced

in

for vitro

fifteen

plasmoidal

not

have

true

was

concluded

effect.

that

than

gross

formation

Since

of

concentrations

Platinum

growth.

this

the

at drug

polyccpheltm

did

rather

by

DNA

[557].

amnine

of Physarum

activity

to

eighteen

results

platinum

more

agents.

bearing

gave

extranucleosomal

trans-platin.

Thirty-five

mice

the

[555].

continue

cells

in plasrodia

anti-tueour

normal

with

false

not

observed

(5561.

of

affected

platinum

in

Lf210

ant-tumour

nuclei

third

without

with

two

Twenty-six

mice

activity

but

also

anti-tumour

1.2-diaminohexane

cell

and

cis-

was

toxic

mobility

was

complexes

less

anti-tumour

clonogenic

with DNA

DNA helix

the

platinum

effective

derivatives

treatment

of

Numerous

electrophoretic

nucleosoral

destabilisation

more

the

complexes

DNA

activity

might

inhibition

of

replication be

connected

DNA

synthesis

C558.5591. TNO-6

shown

was

nephrotoxicity

when

toxicity

in

toxicity

derived

with

human

bound with

from

plasma

leukaemia

a

was

studied Other

by

in mice

active

with

in which

a negative

compatible

L and

charge

[565].

The

aryl

[NO,],

y[SOB]

have in

Crepis

or

active

lower

and

dose

limiting

determined:

[SSl].

The was

platinum

platinum

platinum

diamine

against

or W[SO,])

amines.

the

reaction initially

unit

of

TNO-6

lymphoid

were

of

(149)-(164) was

capillans

more

active

were

used

as

also

L1210

neoplasm

found the

to

acid

be

inhibitors

have (152)

[570]. The

The

[564].

group

a biologically in L1210

egg

in

mice

contafning

derivatives:

stereochemically

[571].

La was

against

inhibitors

In (lsO),

(-)-species

mice

a phosphatidyl

= selenium

(R.R' amino

in

complexes

Encapsulated

active

1.2-diaainocyclohexane

f567.568,569].

than

neoplasm

useful

and

prepared. were

ascorbate

L1210

L2 was

substituents.

containing

were

amine

leukaemia

or

[Pt(RNHZ)(R'NH2)XX']

(+)-isomer also

the

The was

failure

of

the

and

NH3

acid

these

selenium

derivatives

included

fatty

ion,

complexes

Numerous

most

also

ascites

vesicles

groups,

turours

renal

of

other

L' were

and

negative

phosphatidylcholine

or

and

S-180a

against

[PtLL*L2L3]

HPLC:

were

[560].

solid

and

activity

(5631.

Cfs-[Pt(NHa)2(ascorbate)] were

of

complexes

dicarboxylates

anti-tumour

cis-platin

variety

nylosuppresion

[562].

and

halides

with

similar with

compared

patients

to protein

have

to

alkyl

X.X'

= Cl,

[566]. been and

described. (1SQ)

the

dependent, cis-complexes,

isocitrate

These effect

with

the

([lS5),

derivative

was

77

active

against

cis-platin.

Ll2lD but

stereochemistry

and was

leukaenfa.

less autagenic

stereocheristry

the

was also not specified

CT

NH

was

not

and nephrotoxic

specified

in the related species,

than The

[572]. (156)

[573].

,x1

2\

“%a, NH*’ Pt \X2

(149) Xi = ERCOZI (R = alkyl or C&&,Om-iOR). (x50)

x1

x2 = OH

= x' = Cl

(151) x' = x= = OHZ (152) X1X* = [SO,] (153)

X' = X2 = [NO,]

(154)

X'

(155)

X’XZ

= halide,

X2 = glucuronic

NH2b

,x1

NH,’

‘X2

= [SO,].

acid residue

[NO,], or [carboxylate],

x\,” gptLo

0

[email protected]

(156) X.Y = RNHz.

en or 1.2-diaainohexane

lR,2S-[Pt(l,2-diaminocyclopentane)CIZ] conformation: s-gauche active nude

this

conformation

against

mice.

Unlike

Complexes

in

of

in nice;

which CD

active

type

spectrometry

and

rat

not

platinum

were

particularly

prepared

or

nephrotoxic.

a

was in

and

bone

against

S180

[575].

and were

glucuronate

had

tumour xenografts

active

anion was said to be essential

XZ = [SO,]

the x-gauche which

1,2-dianinobenzene

and human

to prove dose limiting

(157)

to adopt

15,2S-complex

had

a

high

15761. (158)

,

anti-tumour

of calf thyaus DNA with the sulphate was investigated

f577].

than the chiral

concluded

it was

thought

the

malignancies

the thiocyanate or

was

than

Bis(pyruvate)

was expected the

X = [NO,]

line MDA-MEI

active

of human

cis-platin

action. The interaction by

more

15743.

a range

marrow suppression

ascites

was

The

complex

ncso-isomer

of

in treatBent

of the human

leukaemia

that in chiral cis-platin

L52222

(158)

was

[578]. However,

analogues.

found breast other

[Pt(diamine)Cl,],

be

less

cancer

to

cell

workers

have

the activity

78 against

P388

configuration

leukaemia of

in

the amine

was

mice

essentially

unaffected

by

the

[579].

(SCN $,

The the

sugar

(X59),

derivative,

presence

S-II,

of

a

Cis-dichloroaquoguanositin anti-tumour Y1,Yz

[NO,].

[R'COO]

specific

anti-tunour

compounds

the

the

site

of

Kz[PtC14]

was

were

Ig

twenty

For

times

‘-P/oNo2

or

the

as effective

H

H

OH

I OH

t OH

I H

tested

in

number

of

vinylamine/vinylsuphonate monomers

conferring

[584].

water

anti-tumour were agents

and

converted [587].

platinum drug

to

Ig coupled

complex

alone

to

[583].

OH

acid)

of

copolymer

polymers the

gave

Polyhydroxylated

solubility

on was

and

the

anti-trypanosomal to

a

H

example,

cis-CPtINHS)t(~to),3EN0932 poly(l-glutamic

the

to

CHO

complexes

For

chemotherapy.

related

Me;

(160)

platinum

of

have or

Anti-turour

than

(158)

A

to

moieties

lymphoma

platinum

in

[589].

(R = H

[582].

targeting

specific

the

synthesis

said

effective

allowed YAC

as

was (160)

dextranamine

more

and

they

example,

been via

RNA

transcription

complexes,

also

toxic

because

alone,

tumour.

have

directly less

of

monoethanol

chelated

etc.).

complexed

compounds

tumour

The

[581].

inhibited

protein

regulatory platinum(I1)

activity

= X.

platinum

preferentially

platinua(i1)

product activity polymeric

been

platinum

used

and

dlamines

dialised 15861. complexes

the to

give

used

a

with

those

of

were

useful

in

sodium

Polyamines and

of

agents

anti-tuaour with

successfully

complex

comparable

results amines

platinum treated

have

[585]. salt

species such as

as

of with (161)

anti-turour

79

The activities were

of cis-[Pt(arino

against

tested

cds-[Pt(GlyOBu),Cl,J

of ADJ/PCG

bad anti-turour

tumour

in

these

viva

I \

[589]. (16S) and (164)

of

tumour

[590]

also

cycloalkylene

alkylidene.

or phenylene

Y

9

o-,“: I I ‘I



X.Y

= NH=.

RNHr.

Cl, OH

Br. NO2 CN or SCN

P O

Y-Pt-x

v/ ’

I

Y

Y (164)

(163) A number

of

trypanocidal

anti-tunour

activity

of Berenil,

1.6.4

with

Complexes

Unidentste

platinum

against

vivo. Complexes

number

influence

I

',P

A

incorporation



w l-6.4.1

I)nlY

x -R-Y

7 \0 0

I

not

(162) Rs,RZ = alkylene.

/”

‘,

did

complexes

MDA-MB231.

activity.

M2

X

line

inhibited

complexes

(5881. (162)

plasaacytoma

acid ester),Cl,]

cell

cis-[Pt(GlyOCMeJ)zClz]

and

However,

'IIthyridine. growth

acid or amino

mammary

the

Group

of studies

Trypaosm

related

rhodcrfcnsc

donor

donor

to cis-platin in

(166). were also prepared 15

amine

corplexes

vitro

but

showed not

in

(Scheme 3) [591].

ligands

ltigands

of the biological

effects

of cir-platin

and related

80

complexes

have

a number

reductase.

and

dehydrogenase inhibition

essential was

caused

of

been

not

particular

directly

of enzymes

dihydrofolate and

fuaarase

fumarase

methionine

was

reductase could

dominated

at the active

by reaction

with

related

including

to

their

[593]

distinguish by

anti-tueour

U-lactarase were

site, whilst

two thiol , groups

inhibited.

cis-

interaction

and

with

In

Both

malate The

trans-platin. the SMe group

that of malate near

effects.

15921, dihydropteridine

the enzyme

of

an

dehydrogenase binding

site

[594,595].

%N&NH,NNN=g fast (1-1

+

Kt[PtC14]

-----+

[(lbS)][PtCl,]

Ar

‘Pt a’

Scheme 3 Reactions

Af

\p~_f/~N/

of Berenil with Kr[PtClbI

15911

\

’ (3

81 Cis-platin being

reduced

proliferation

the

induction

of

increase

the

viruses

inactivated

containing

was demonstrated In human of

the

cells

platinum

administration

revealed nucleoli

that

and

it

at

platinum

electrodes

by

classical

or

A

a01

[604].

were

the

neither

but were

type

toxic

to most

were mutagenic

was

entropies of

of

[M(NHs)4]Zf

of the

ammine

type

solid

I.

phase

the of

detergent.

The

stranded

RNA

in sheep

phase

cis q

mice and

presence nucleolar

after

the

cis-platin

chromatin

and

[600]. Cis-platin

by

chloride

its

assisted

trans-platin

could

with

a

be

detection

gaseous

(M = Pd

or

metal

the

Pt)

have

[55].

complexes

species

for

The

typhimurium

including

fn

been

damage

effect

repair

including

of the geometric chromatography

were

was

was and

{SOS].

reviewed,

on RP in paper

cis-isomers

BuNH,

in excision

considered

the

ineffective

Cis-[Pt(arine),Cl,)

deficient

to

trans-labilising

and repairable

ions

shown

Trypanosoma

was

Salmonella

of some amines strains

was

with

cis-platin

in propanone.

towards

acid

infected

(L = strong

towards

Corplexes

planar

and

CiS-

greater

than

that

[606]. of

[Pt(NH,)4]Cl

transition

ligands

which

in the

testis

polyglutamic

noted

mutagenic

the Rf value

The heat capacity

of

enhanced

in the

polarography

in

was

bacteria

only

among

for the trsns-analogues

a

of

activity

polyatomic

of square

discussed;

grown

Cis-and

pulse

that they caused specific

trans-[Pt(RMiz)rXz];

indicating

to

interaction

double

in

cricket

[Sol].

complex

nor

PhCH(Me)N&

ntechanisms, implying

configuration

markedly

of viremia

of platinum

cis-[Pt(arine)LCl,]

toxic

but was mutagenic.

discussions

a

concentrated

voltammetrically

ratio

less toxic,

The

of vessel

[4302,603].

therapeutic

OP

be

the

differential

trypanocidal

A high

Complexes

ligand)

of

and

concentrated

of

quantified

platinum(I1)

substantial

congolense.

dmso,

be

1-l

cis-diammine a

the

treatment

(Wl-BBVAD)

to

was

lysosymes

determined

have

orbi-

of the distribution

oxidation

could

lo-=

presence

the

damage

by

of

microcultures

Caffeine

prepared

the

of

Pound

serua

of

in

in culture

in blood

limit

cultures.

be

Bluetongue.

was

An EELS study

chromosomes,

leucocyte

cytogenic

reasons

inhibition

and retardation

peripheral

the

cfs-platin the

cells,

the

rats,

proliferation,

enough

could

effectiveness

transformed

[[email protected]@].

of

in

[[email protected]].

cis-platin,

region

human

indices

with

The

tissue

produced

Vaccines

included

species.

of

hours

(5971.

enterostomies

and endothelial

micronucleus

action

non-enveloped viruses

for 24-72

of

connective

[[email protected]]. Treatment

crs-platin

mutagenic

healing

of fibroblasts

proliferation with

worsened

in both

usually

at

measured

K.

The

a

change

cruns-transformations

of

over

the

potential

was determined.

phases

involves

t was

146.6

of

The

crystal

range

barrier phase

have

rotation

transition

structure

[Pt(NH,),Xz]

87-26'7 K.

to

[SO?].

been

was The

studied

82

[SOS]. The

decomposition

@‘t(NHs)&Izl

t

contrast,

at

[Pt(NH3)4JClp

7 mm

trans

the

[Pt(daso)(py)Clz] dependent,

of

but

to

an

on

of

[Pt(NHs)r]Clr

investigation

of

the

decomposition

reactions

been

studied

[58].

then

Pd metal

of

which

mixing

[Sll].

was

Both

[Pd(N&

not entirely studies

trans-[Pt(NHs)tX,]

C613.6141.

[612].

excellent

[CN])

Electrocherical

synthesis

has

(23)-(25))

been

trans-[Pt(NHs)zC1,] kinetics

of

with

of the reaction

trans-[Pt(NHs)ZClr]

thiourea. were

in tu,

gave

+ KI 7

as

[SeOl12hydrolysis of

of

transition analogues

of

state

with

reaction has were

of

The

two

also PdClz

the

thermal

cyanuric

acid,

by

of

a

INOzl) 9

or

have

I”-

[Pt(N&),Cly

[615]. in

three

steps

(reactions

Reaction

[6x6].

trans-[Pt(NHg),(tu)Cl]Cl,

of

and

the

) trans-[Pt(NH,)z(HZO)C1][NO.]

(24)

[Pt(NH,),Cl]Cl

of

[Pt(en)tCln]

The and

on

[Pt(en)Cl,]

the

Pt-OH2

was

I)

with

volumes were

aquation

bonds

(25)

[Pt(NH9)+]C12 (sic

activation

studied.

properly

a catalyst exchange

[Pt(NH,)z(NO,)z]

been

[Pt(NHz,) alC1, give

pressure

have gave

catalysed

oxidation

constants

and

[SlS].

cis-[Pt(NH,)&lz]

thermal

(curiously

the

determined A

velocity. inferred

by

Be-

Cl-.

for

first

from

and acid

a study

hexacoordinate comparison

with

[SlS].

conditions products

tranl)

The

an

(23)

association

and

the

and

[617].

%

determined

effect

the

The

cis

were

of

[NH,1 EOHI

HCl.

described

study

trans-[Pt(NH,)&lI]

trans-[Pt(NHs)2(HaO)Cl]+

sphere

and

pressure

hydrogen

[610].

In

Hz0

Ag[NOS],

outer

give

'C.

cis-[Pt(WeNH,)$lz]

detail

investigated

trans-[Pt(Nlio),CII]

The

or

and

[Pt(NH,),Cl]Cl

described

or

(X = [SCN]

(x = o-4. y = o-4, n = -2-+2) have been undertaken An

Another

)4]Clz

cis-[Pt(NH,),X,] or

not

[Pt(NH3)z(N0,),]

elucidated

to

193

trans-[Pt(NHB)rClr]

carbonate

[SCN]

was

salts

hydrogen

of

(X = [NO,],

described

rhenium and

'C

[Pt(dmso)(NH~)Cl,J

[SOS].

of

and

at

in oxygen

decomposition this

204

temperature

heating

[Pt(NHS),][NO,],

at

initiated

of

the

with

began

was

mechanism

involved

aminoguanidine

Polarographic

been

of

and

sphere

of

Thermal

or PdO

decomposition mechanism

effect

1 atm

isomerisation

melting,

inner

decomposition

at

decomposition

cfs

occurred

implying

Hg

of

was for

with

This

was

characterised trapped

the

in

and

acid complex,

under and

a

range

few

of

of the

[107.173].

vesicles

photocatalytic

fPt(NH3)*]*+

phosphoric

extremely

H+

and

reduction on

reduced of

a-zirconium

to

water

platinum

retal

to hydrogen

phosphate

was

to

[620]. studied.

83

This

found

was

C=ll.

to

be

easier

CPd(@JH,),lIBPh,lz

used

in

a

photoimaging

comprising

a

layer

conductive

support

preparation

composite

l-2 M

media.

other platinum A number

lead(I1)

been

activated

with w%s

especially quantities

of the type Among

I-aminohexane

[627].

used

but Kurnakov's

of PdCl,

characterised under

by

X-ray

strictly

cis-[M(pyrrolidine),X,1

were

the structure In anions

an

first

step

the

[624]. palladium

the

for

in

from

extraction the

aliphatic

presence

the

amine

[ML,X,],

and

of of

[RL,X]X

and

CPtLxClz 1 characterised; the

iodo

the

of

corplexes

of

ospovaccinia

ligand.

that the chloro

hydrolytic

prepared complex

and

were shown

(R = Pd

characterised

was not fully defined.

X-ray

diffraction to be packed

study

of

gave

Since

conditions

cleavage

[PtLBrs].2Hr0

lC

at 80-85

diffraction.

anhydrous

complexes

In the

as

in (Me=N),W

involved

CSCNI)

its

trans-isorera

prepared

test suggested

mechanism

[631].

[623].

virus

[628].

complexes

corplexes

had

adopted

16291.

Thermolysis successful

electrically

element

extract

with

and

the

w%s

layer

an element

(M = Pd or Pt; X = halide)

[626],

cis-

Both

against

which

to

primary

was

trans-geometry

as

support

catalyst-electrode

palladium

[ML,X,] the

When

cfs-geometry.

and

be

[625].

of

sugar

an

recording

useful of

were (186)) weak activity

amino

on

)s]'+

a cerret with

[Pt(NHS)IC12]

used

(L = 1-aminocamphene, cis-compound displayed an

and

photoconductor

membrane

described.

those

layer

involved

[Co(N&

and could

conductive

and combined

electrolysis

proved

prepared

electrically

membrane

milligram

of complexes

were

oxide

with

properties

a subbing

trichloromethane

group metals

being

An

exchanging

ion

This

reaction

and a surfactant.

water

in

and

have

synthesised

IML 1xz

for

micro

monoamines

a

an

aniline

HCl

submicro,

[622].

of an ion exchanging

N-Butyl

related

to give an electrically of

useful

impregnation

of

the

photothermographic

terephthalate).

[Pd(NHo)+]Clt.

containing

The

system

a poly(ethene

was coated with

than

exhibited

it

was

(MezN).PO or

by

in which

Pt; IR

to

X = Cl,

and

L was

trans-[Pd(Me2NH)tC1z] the

reaction

not

that

the

[630].

The

presumed Me,NR Br,

electronic hex-ethylene

but it may well be polymeric of

was

I.

[N&l

spectroscopy tetramine. (6321.

cir-K,EPt(NH,CHtCHtSOS),C1,1.3H~0

into the crystal

in columns

with

or

the

significantly

different

platinum-platinum

The

preparation

trans-[PdLZClr]

nitrogen was

atom

2-.

group

DTA

18353.

groups

The

(167)

bound

(168)

species

but

16341.

In

were

were

with

also

were

[633].

characterised did

not

to

bonded

in

through

platinum

by

indicate

trans-[MLIXZ],

was

and

[PdL,]ClZ,

were

and

bonded

complexes

[640].

A

R = 3-N&

was

Some

[PtL,]=+

IR

which

which

the

through

L

amino

the

-NHZ

simple

a

the

at

only

cfs-

tranr-CPtLz(NH3)t]Clt

have

been

the

involved

IR

pyridine

nitrogen

in extensive

the

atom

in

in propanone.

coordinated performed spectra

via on were

the

the

sp'

complex anaiysed

X-ray

(171), in

of for

atom, which

great

of

imidazole) of

added

salts from

prepared 2.3-direthyl

of

nicotinamlde.

indicated although

and

Complexes

[641].

[PtL4]Clt

cases,

or

derivatives

be the

data

that the

binding

amide

group

18421. was

diffraction

nitrogen of

reaction

cio-[Pt(4-NCpy)zClZ]

complexes and

all

bonding

of

could

spectroscopic

hydrogen

2-Mepy

presence

but

rrans-[Pt(1-ethenyl-3-rethylpyrazole),C1Z] ligand

by

by

as catalysts

Related

reaction in

polymeric

cla-[PtLZX*].

involved

Q = py,

N(4))

gave

and

monitored

ligatuis

cis-EPtL&l*l.

(coordinated

prepared.

formed be used

amine.

The

study

ligands

(l(EB).

donor

neutral

[SSS].

kinetic

complex.

being

on

Similar

16381.

(L = thiourea.

and

reaction

could

trans-isoner

spectroscopy.

species

but

the

NQR

the

the

nitroSen

reported to

2,8-diaethylpyrazine

of

to

"'1

bromides,

to nonoenes

also

by

characterised,

cis-[PtL,Q,]'+

were

converted

followed

[637].

subjected

2,5-direthyl

(168)

hettrocyclic

from

was

R = 2-NH*

related

poorly

Unfdcntatc

prepared

tu

for

of dlenes

methylthiourea

the

A)

authors

ligand

(167)

being

spectroscopy

1.6.4.2 The

reaction

observed

RN&

hydrogenation

was

the cis-

the

cis-[Pt(BuNHP)ZIz]

the

7s~e'13r NQR

with

and

4.70

complexes,

The

4-aninobenzonitrile.

complex

processes

were

described.

TG q easurerents.

metal

and

16361.

therrolysis,

PdCi+

been

and

was or

3-,

(3.22

2-aminopyridine

of

has

spectroscopy,

distances

data N(2) was

detail

[6433. also

from

prepared

showed

N(2)

[644].

the A

ligand. sirilar

coordinated. The

PdClp

and

(1'10). was study The

structure

was nmr of

85

tr..rts-[Pt(pzl)r(PPha)2], tPt(dppe)(pzl),j

with

was

tl=B.

also

[CpRu(PPh9)Z(MeOH)l*

[(dppe)Pt(~-pzl)zRuIPPhs)Cpl[sPh41.

but

disproportionation

yielding

ICpRu(pzl)(PPh,),l

16431.

the

known

reported did not

give the

instead

the

compounds

w

C6453.

Reaction

desired

complex

of

complex

underwent

[PtZ(u-pzl)Z(dppe)Z]z+

and

0

0

""2

(1-1

(1701

(1711

(172) (Reproduced Reaction cis-[PtLzIzJ,

of

l-propylimidazole.

characterised

[64'73. Other

workers

found

less

to be

calcium nitrated

and

magnesium

((173) = risonidazole)

by

reported

good

irldazoles

site of metal

with permission

with

and RI gave R*CPtCl,l and conductivity leasurerents

IR spectroscopy related

inhibitors dependent has

been

an

X-ray

coordination.

L.

from [6451)

cis-complexes

than

oxazole

conplexes

ATPase

[648].

prepared.

In

diffraction

All the complexes

of palladium.

A

These were

of membrane

range

of

bonded

corplexes

of

eranr-[Pt(aisonidazole),Cl,

study

established

were roderate

N(1)

as

]

the

radiosensitisers

86 with low toxicity

CS4QJ.

(1731

Raman

IR. structure nitrogen

and

and atom

was

{Pd(oxalate)L,}, Or

'H nmr

bonding platinum

related

Tocicity the

data

7-azaindole

Coordination was

were

or

no

range

N-Et-

anti-tumour

and although

tests (X = Cl

toxicity

action

and dmtp acted as a monodentate

the

corresponding

ring

system.

It thus

[781.

[SSS]. reduced

Benzotriazole The

fog

in

without

a

[Pd(177),]Cll

(174)

resembled (BTAH).

a

black

and

decrease

to the developer

to

guanine

(1761, in

was

white

or

The

complexes,

2-Mebenzoxazole soluble

dirers.

N-Pr-imidazole

have or

or

been

considerably, The

than

silver

(6541.

(175)

halide

there

structure

of

diffraction

(175)).

The

tQCR1

ligand binding

through

of a purine

adenine

N(3)-coordinated

photographic

for

X-ray

the N(Q)-nitrogen rather

reported

I or XZ = oxalate).

varied

ligands were S-bonded, nitrogen

palladium

[652-J.

established was by IPt(drtp)~lCPt(6CR),l (dmtp = 5,7-dinethyl[1.2,4]triazolo[l,5-a)pyrimidine,

triazole

the

[SSl].

cia-[Pt(174)ZXz]

anti-tumour

of

sparingly

as

L = WMe-,

preliminary

via N(7).

A

3.5~Mezlsoxazole.

characterised

were monomeric

complexes,

was

little

and

16503.

(n = 2.

complexes

3-amino-5-Me-isoxazole)

bound

investigate

trans-[Pt(oxazole),C&].

and

L = isoxazole,

(n = 1,

2,5+le,benzoxazole)

Other

CiS-

used to

were

spectroscopy in

or hypoxanthine

in

[Pd(BTAH),Cl,] film

was

addition

of

radiographic

sensitivity

fused

by

87 Palladium ring

opening

ruptured

of

complexes depended

in all

the

on

cases

type

the

(178)

have

substituents.

been

with

investigated. the

C-N

The

single

rate

bond

of

being

[655].

~J$L~~2

CI (178) Reaction X-ray

of

PdClz

diffraction.

formed and

from

This

(180),

I-6.4.3

Bidentate

rethod and

been

furnace,

for

tissues

followed

the

of

This by

polydentate

was

dissolution

forred

the

(179). vis

characterised

the

with

triaxole

by

ligand.

[Pd(cyclooctene),Cl,]

coordination

sphere,

yielding

[656].

with

permission

amine

the or

be

gave

However.

in

(182)

patients

to

azide.

(Reproduced

and

cyclooctene

place

and

determining

developed.

with

presumed

and

(181)

(179)

has

was

took

reaction

PhNo,

plasma

PhNs

cyclooctene

sucessively

A

and

total

donor

in

on aqua

drying

[SSS])

ligand6

platinum

experimental

based

from

content

animals and

regia/HCl/en.

in

urine,

receiving

combustion This

gave

blood

cis-platin in

a

ruffle

a platinum

complex

of

1.2-diasinoethane.

which

could

be

detected

by

pulse

polaraography

[657].

[la11

(180 1

I1821

The

electronic

were

calculated

with

anti-tumour A

range

that

of

However,

for

related

the

the

to d,z_Yz of

the

Complexes

of 88

the

[SSl].

the and

growth

of

Treatment

pyridine product

gave was

The

was

palladium

in

water

in

and

CD

which

spectra

to give

structure

{RR+SS} the of

The

via

spin

electroplating;

allowed

implied imine

SS-form

that

by or

with

human

implied

[PdCL,12-. amine)

dd bands

to

the

[659].

gave

species

amine

the

X-ray Bu)

with

reacted

structure

of

diffraction were

R = H

and had

synthesised

had

the

best

cancer

in

effect

cell

Tl[OOCC,H,] The

the

[SSO].

structure

line

in

hot

of

the

[SSZ]. be

[Pd(l.3-pn)Cl,] baths

the

7 breast

MCP

= (185))

diffraction

electroplating

for

L.

complex,

(R = H

(H,L

described

prepared.

These

that

(L = monodentate

two

[Pt(H2L)(py)r][OOCC,p,l.

by X-ray

to

1.2-pn.

were

measured.

similar

established

[Pt(H,L)Cl,]

was

an

dependent

1.3-pn.

EPta(PhCN)4(L)*Cl,l

(184)

forms.

hormone

[Pt(py),L]

1,3-pn

being

correlated

[658].

Me&NHCH.CH,NHCMeB.

data

give

complexes

were

L = en,

were

was

with

diamine

indices

indices

crans-[PdLzCll]

split

to

(183).

gross

typical

platinum

or MetN(CH2),NMez

orbital9

species

nitrile

established

ligand

in

EttNCHpCHINHt

d

of

Electron

IPt(PhCN)(LICl,l,

species,

meso.

RR.

[PdLCl,]

IR spectroscopic

coordinated

mononuclear

range

therapeutic

magnetic

stoicheionetry

with

and

metal

band

a

method.

cls-[Pt(PhCN)&l,]

Cpt,(PhCN)a(L)&l,].

on

and

of

Reaction of

LDsO

complexes

pattern

dua

of

CNDO/2-SCF

HMeNCH,CH,NHMe. absorption

the

d xz and

the

activity,

HrNCH&HtNMel. Electronic

configurations by

a

useful

readily

was

[663].

complexing

A

range

agent

soluble of

corplexes

for

both

in

(188)

89

(R'. X2

R'.

R4

R3.

was

= fOzCCHrC02])

anti-tumour

effect

anti-leukaemic

mice

compound

was

(187)

it

interested

(and linguistically

the

original

X = Cl

was

described

paper

or

Br)

with

(M(188)Xz)

was

shown

as

gave

monomeric

(188) (Reproduced

1.2-Diaminocyclohexane structures

of

determined

been

compounds

has

with

of

C687.6681.

The

x = Cl showed

given

for

or some

a

[NO,] or Xz = glycolate derivative;

piperidine

Reaction

mixture

be well-advised of Kz[MX4f

(188)

acting

or the

to consult

(M = Pd

and

{M(188)X,}

new

or

Pt:

[M(188),]X,.

as a bridge,

but

the

[SSS].

with permission

been

a

from

popular

[Pt(R.R-1,2-diaulnocyclohexane)X] by

or

reader would

to be polymeric

other complex was probably

have

a

structure

aminomethyl

[6653.

arylalkyl; the complexes

the

(X = halide an

adept)

in Japanese (188)

Although

[664].

pyruvate)

or

and characterised;

prepared

in

cycloalkyl

alkyl,

= H.

X-ray

diffraction.

related

bis(pyruvate)

[660])

ligand

(X = oxalate Both

were

derivative

year.

#is

or

[OOCCH,COO])

useful was

The

shown

anti-tuaour to act

as

90

an

immunosuppressant,

blood

lymphocytes

and

inhibited

[669]. An X-ray

diffraction was

configuration

transformation

by phytohaemaglutinin,

derived

ligand

the

[670].

[PtL(NRB)I]CPtC1~]

study

coordinated

of

pokeweed

Electronic

dd transitions

bands

induced

by

state.

Optical

activity

intermolecular

and

CD

peripheral

concanavalin-A

the achiral in

spectra

biphenyl

a

x-chiral

of

[PtLClz].

(L = R.R-1.2-diaminocyclohexane)

of the chiral

and

was also

that

or

stereospecifically

absorption

and fPtL(NHS)z][PdC14]

the region of singlet

human

mitogen

(1Se) showed

entirely

of

species

interionic

induced

showed

interactions

very

in

in the dd transitions

in

strong

the

solid

of the anions

[671].

Hovm RHN,

F*HL&F

,NHR

c.$p’\ CI

F

F

F

(181)

(185)

(1-1

(187)

EdtaH, was shown palladiun(I1)

to inhibit

[672].

Two were

methods

baths

of the excess of edtab

[Pt(edtaH,)L]Cl,. measurements prepared A

with

characterised

[674].

The

the

determination

on chelation L

complexes

with

IR (190)

and and

spectrsocopy (191)

solution

palladium at

of in

pH 10. and

[673]. The reaction

bipy

1.3-pn, W

of

[edtaN*]]'-

with 0.1 M Zn[SQ]

(L = en,

by

in an aqueous

(M = Pd

or and

gave phen) conductance

or Pt)

have

been

amine8

and

[675].

number

related

based

C oxidation

for

electroplating

cfs-[Pt(edta&)Cl,]

(1-1

vitamin

back titration of

F

of palladium

species

with Kz[PtC14]

and

platinum

have been described. to give species

derivatives

For example,

with a platinum

of

polymeric

polyetheneimine

loading

was reacted

of 40-50 X. The use of

91

such complexes

may reduce

also have

targeting

some

the toxic effects

and

poly(N-ethenylpyrrolidone)

of

proved study

useful

as

of the

Al75

led

to

also

evidence

the

as a polymer from

that

for bis(diamine) thermal

on

(192)

chelated stability

RNIINHz. It

and

planar

chemotherapy

platinur(II)

and may

derivatives

poly(N-ethenyl-5-methyl-2-oxazolldone)

catalysts

of PdCl,

conclusion

of good

Kr[PtCII]

lines

hydrogenation

complexation

of platinum

[676]. Square

value

showed

and

the

anti-bacterial

surface

had

been

species with some

of dien

formed. [678].

[677]. A Aerosil

However,

(193)

a molecular activity

agents modified

was

was synthesised

weight

against

there

of

lo'-104.

turoural

cell

[679].

(lm)

(Reproduced

1.6-diarinohexane 1.4-diarinobenzene.

were

polymers

Organoretallic or

urea,

Mass

with permission

or

from

spectroretry

from

prepared Kt

was

[PdCl*] used

[870]) KzCPtClJ 1.6-diaminohexane

from and for

characterisation

of

and or the

92

materials

[680].

Related

complexes

were

tested

for

antibacterial

activity

[SSlJ.

(HOOCCH+HN

NHKH2COW ‘i /\ Cl

0

NH

NH

f-

Y

-Q-

0

Cl

H NCH2CH2NCH2%

..

;‘rf

/ N

\ /NH2

h I\

0

(193) There

have

conplexes.

been

1.1.7.7~Me,dien a

more

Anation

given

or

L

the

second

deviations conjugate

were

base of

studied

depended

which

above

containing

substitution

on

and

complex

pH 9

due

of

[PdLCl]+ by

temperature the

and

&v*

values the

to

substitution

to kinetic

the

The

were were

only

or

or

aquation

of

the

of

subs,titution

iodide

pressure. increased.

R

ion

The There

consistent

of

were

rate was

the

and

reverse

groups,

but [684].

with

hydroxo

= Cl-.

order

species,

of

Xn-

For

the

reactive

kinetics Et;

dien

analysis.

in

intervention The

of

(L = 1,4,7-Et,dien.

(L = 1.4.7~Me,dien.

hydroxyl

substrate

type

was

[683].

independent

of (36)

cosntants

(R = II, Me

nature

kinetics

subjected

rate

species

the

almost

1.1.4.7.7-Mesdien)

in

were

spectrophotometrically.

were

nucleophile.

ns*

aquo

[Pd(RSdien)X]*-"+

strongly

constants

hindrance

the

occurred

solvolysis

the the

order

&.

in

of of

1,1.4,7,7-Me,dien)

X=C1
reports

reactions

and/or

spontaneous

Br-.

I- or

anation the

The

constants very

as

rates

kinetics

a

decreased

strong

py)

equilibrium

1.1.7.7~Me,dien studied

a but

or

function as

evidence

of

of

steric in

the

93

values

tW*

for

substituted mechanism

dfen was

[PdL(H20)]2'

associative

X-

[PdLX]+

redox

and

photophysical

complexes

bridged

cyan0

nucleophiles.

+

inert

destroy

original

the

Its effect

was

limited

redox properties

to

The liquid extraction

major species The

important Reaction

a

the

aprotic

the

of gave

(195). gave

in

the

polymeric

palladium(O)

hydrogenation

and

complex

to the

was

did not

chromophore.

lifetime,

of bipy was

energy

and

were to

(199).

but

(194). Reduction

was

a

good

chloride

of

studied.

the

in

with of

the in

It was shown that

departing not

hexachloride

effective,

[689].

substitution

complex.

which

very

[Pd(bipy),][BCls],

ethanenitrlle

species,

moiety

ruthenium

by cobalt dicarbolide

assistance

bipy

from

platinum

[688].

nucleophilic

solvent

substituted

of the

modifications

state

phase being

anchireric

controlled

prepared

newly

this functionalisation

(am = F&NH* or HOCHzCHzNHt)

CPt(bipy)(am)Cll+

two

of

aynthesised

properties

in the presence

the

of

(28)

the added

of view

of palladium(I1)

in the organic

kinetics

solvent

slight

= (BCls])

the hydroxyl

CSSS].

properties

point

state

of the excited

([(CZBSHsC13)ZCo]

with

reaction

C(CN)(bipy)~Ru(CN)Pt(dien)l~ClO~l~

from a redox excited

However.

the

ethyl

Hz0

C(dien)Pt(NC)(Ru(bipy)t)(CN)Pt(dien)]tClO~l.. [Pt(dien)Br]Br, were investigated 1887). Since essentially

Related

again

investigated:

was also important

-

[SW].

mechanism

also

for rost

base mechanism

+

reaction

were

derivatives

associative

ion a conjugate

The

an

chlorine methanol

the (196)

was [890].

diisocyanate. with

catalyst

for

LitAl&] alkene

[SSl]. 0

2

NH2

hi,

+

;o N

\

jN

NC0 (OPE10Me12

Reaction

of

gave a red species

[Pd(5-NOzphen)t][C10~]z which was unstable

with

I-axinopropane

both therrodynamically

or

piperidine

and kinetically.

94

Attack

of

Treatment

of

the

at the The

occurred

related

In

CPd(en),lCl,. and

amine

the

this

5-NOzphen

complex

case

the

ligand

to give

techniques. disorder,

forms

was

fast

(198)

was

still

X-ray

distorted boat

dioate

of

gave,

en

at

directly

complex

(Reproduced

prepared

'C

the

[692]. ultimately palladium

[693].

of

spectroscopic r and

the

study.

The

complex

studied

and

a

by

bridge

two at

-99

'C

chair [694].

structure

at

six-membered precursor

X-ray showed

possible

its

coordination

the is

the

timescale

ligand.

and

and

-CH&HZ-

interconverison

planar, The

complexes

was

platinum

was

chelate to

a

ring

series

of

[695].

with

cis-[Ph,Pt(dnso),]

be converted

(FIX,) was (HgCl,),

was

-115

PdCl,

square

conformation.

(197)

could

nmr

diffraction

an

propane

which

the

the

by

C-bonded

Reaction

on

and

from

a

with both

a Meisenheimer

at

synthesised

tetrahedrally

attacked

(1971,

Even

crystallographic

adopted

phenanthroline

[Pd(S-NO,phen)Cl,] diamine

diaminopropane-N'.~")FtClz].HtO.

elucidated

coordinated

[({1,2-bis(pyridin-2-yl)-ethane-N.N')-2.2-dimethyl-l,3-

complex

diffraction

the

at

with

to a series

(MnClz} or {PtPh,)

permission

bipym,

from [694])

4199).

of biaetallic [696].

gave

species.

[PhzPt(bipyr)l, (290)

in

which

95

0

>y$&Mx2

w

(MO)

(:189) Interesting

bimetallic

complexes

could

also be obtained

using

the ligand

(dppn) (Scheme 4) f697].

3,6-bis(2-pyridyl)pyridazine

CH2ClZ/X-

CEr(NO)(dppn)(PPb,),]*+

X =

\

[Pd(PhCN),Cl,]

Cl, Br or I

\

PPh,

q&2$ c/‘\ I

Scheme

Preparation

lr\N/pd\cI I II c’ 0 interconversion8

and

3.6-bis(2-pyridyl)pyridazine

The

structure

was

to

[SSS].

which

preparation

by X-ray

was of

planar,

of

transformed

K,[PdL(CN),]

and

X-ray

since

diffraction

its

donor

study

the

suggesting and

may

reaction

to

that

by

Mz[PtL(CN)z]

ability

The ligand might

complexes

of

be

of [BURN] z[PtL(CN)z]

ligand

be

with

.addition

PdCIL

shows

useful

gave

dppe to

showed

little chIral

aim

was

expected

at

a

of

as

M =

an

the

2-cyanopyridine

(HrL = (201); as

with

The coordination

the

therefore

(209)

of

techniques.

[Pd(PPh,),(N,),]

been deecribed. has CBu,N]) 4.4' .5.5'-tetracyano-2.2V-biimidaxole cyanides,

by

bimetallic

[697]

diffraction

coordination

Reaction

of

(dppn)

prepared

(201),

essentially

resistance

auxiliary (202).

of

was established

palladium steric

Cl-

N,pdlc’ -

4

ligand.

Q&-p

MeCN. PPho

[899]. K.

[NH,] use

alternative to

be

distorted

or the

to

comparable. square

The

two An

planar

96

geometry

at platinum

and -a platinum-carbon

tetracyanoplatinates. L than for anions,

This

a slightly

[CN]. The size of the cation

and partially

molecular

indicates

chlorine

oxidised

bond distance

compounds

lower r-acceptor

prevented were

the stacking

not obtained

P(OI%)o

and

(206)

All these

nmr spectroscopic (207)

amino

to

be

with from

a

to give

syn-

or

An

analogue

of the planar

on treatment

with

(205) for L = PEtS

gave

of (M)

interesting

sensitive

and

was

dynamic

selective

of palladium(II),

Although

it was not made

atom

(m)

[703]. Complexes

LH =

for

prepared

behaviour

from

on the

[701].

determination

PdCl*

with Na[Bpzl,l

showed

and an azo nitrogen

not delineated forred

L = Et2S.

complexes

in tic1 solution.

group

reacted

for

timescale

proved

spectrophotometric complex

capacity

t-1

of tr~ns-[{PdLCl(u-Cl)}~]

[Pd(en)Clt].

in the

dwe

(202)

or

than

[700].

-

Reactlon

shorter

but

seems

anti-(210)

with which clear.

probable

the precise

of stoicheiometry (R = Ph

reagent

the a 1:l

through

ligand

an

(208)

of the reaction

[PtL(RL)]Cl

or Me).

it formed

binding

[702]. The

course

for

was

and [Ptt,] were

Although

the

mode

of

97

bonding used,

was the

discussed

[PdLCll of both of

the

atom,

and

structures

amid0

(211) and

NH

was

thus altering

it seemed

were

not

certain

fully

that

(212) (LH) the l&and

promoted

by

both

established

metal

nitrogen

17041.

In

was tridentate.

coordination

the more usual O-ligation

to

of aaides

B/

complexes

including

the

complexes

studied

the

pga

palladium

of

of

tetraaza

derivatives

of

ligand

complex

of

and

(212)

0

the

(212).

the the

other

nitrogen

0-N\

WC12

N

tetradentate

by UV spectroscopy.

the

Deprotonation

Cl +f

More

were

conplexes

[705).

ZN-N'

CI

atoms

the

macrocycles

Pyridine There

stablity palladium

derivatives

was a linear constant atom

have

WAS

of

been

gave

reported,

association

correlation the

corplex.

postulated

between In

to occupy

the a

98

position

above

five-coordinate

the

plane

complex,

the

of

It

ring.

but association

was

of a sixth

thus

easy

to

form

a

ligand was nore difficult

[706].

(211)

R = 2-NH2

(212)

R = 3-N&

(213)

1.6.4.4

An

Porphyrin

increased

porphyrin

and

number

complexes

photochemistry

has

Phthalocyanine

of

studies

been

and photophysics.

[Pt(TPP)] have been determined. and

the

evidence

B-hydrogen of coupling

and

Complexes

Wcarbon

of

palladium(II) with

published,

many

and again

The 'Ii and 13C nmr spectra In [Pt(TPP)] nuclei

to the a-carbon

of

centres

of

there was coupling the

pyrrole

17073.

The

platinua(II) dealing (Pd(TPP)]

with and

between *ssPt

rings, migration

with

some

behaviour

99

of

metal

the

investigated: structure to

be

of

complexes

of

palladium

[Pt(TPP)]

isoaorphous

complexes.

The

alternately

above

The

with

energies

by

which

transitions

solution

were

of

(and

conrplexes

with

in terms

which

in

the

transition

and

Soret

palladium

using

of

and

absorption

The

shown

palladium

and

donors

17093. I have

in

dipoles

bands

the of

the

W+W*

Monomeric

derivatives

in

Raman

been

orbital

[710].

resonance

and

it was

nitrogen

shifts

platinum

been

17081.

uroporhyrin

caused

the

a-

TPP

derivatives

of

other

constants

were

Epr

spectroscopic

the

electronic

reflected

in

the Pd-N

for [Pd(TPP)]

and

data.

with

determined

to

in

ntetals) forms

(214).

of a U--I interaction,

changes

spectroscopic

were

the

derivatives

and

the

complex

has

study

copper

with

the

Diaerisation

change to

of

4.6-dinitrobenzofuroxane,

Association

resulted

a

both

studied

described

nmr

of metal

rise

nickel,

ruffled

plane

the

diffraction,

cobalt.

mean

in

HPTLC

and

aqueous

difference

[711].

[Pt(TPP)]

donor.

to

give

X-ray

was

spectroscopy.

led

forms

spectroscopy

the

structures UV

that

aggregated

nucleus

below

by

iron,

the

included

was

determined

porphine

electronic

investigated

derivative

was

and

in

tetrakis(4-methyphenyl)porphyrin

from

data

optical

suggested of

molecular

association

the porphyrin

structure

o-bonding

The

I:1

the

17121. Similar

could

complex

as

absorption that

be the

and 'If

r-conplexation

central

metal

data were

atom

obtained

(215) [713].



The

redox

chemistry

by electrochemical of TPPSH,

of water

and pulse

and tetrakis

soluble

radiolytic

N-methyl-4-pyridyl

retalloporphyrins

techniques. porphyrin

has

The palladium were

been

studied

derivatives

investigated.

Under

loo

both

electrochemical

were

formed

study

[714].

the

and

radiolytic

Voltamaetric

electrochemical

conditions

and

epr

unstable

spectroscopic

behaviour

of

free

n-radical

methods

radical

were

complex.

potential

of

The presence

the

complex,

with the porphyrin Kinetic

of the radIca1

implying

w-system

the

have

been

ion-dipole

reported.

association

These

of

a

free base N-methylporphyrin, bond

formation

displacement dependent, The

the

complexes

was

epr

showed

study

Quantum

Fine

yields

using

organic

polarization derivative to

group.

of

in the redox

could

be

coupled

reaction

of

and

and

the

the

of ligand dissociation

and

invoving

[Pd(TPP)]

[716].

zinc(XI) epr

nucleophilic were

and

solvent

palladium(I1)

spectroscopy

17171.

on the values

of the

The zero

[718].

of

several

with

details

triplet

or

dmso

involving

complex

kinetic

its

MeCN.

mechanisa

porphyrin

of dimerisation

formation

for

in

a

step

Whilst

TPPSg

optical

singlet

palladium

fluorescence

spectra films

the

excitation

laser

spectra 'Alg

between

and

oxygen

were

complexes

of

the

state

in

lowest

measured

of water

and platinum

allowed

the

to relate

authors

FAR

w-system

3EU

[720].

state

emission

porphyrin

in

soluble

porphyrin

(and

ions and

of

a

platinum The decay

spectrum

was

complexes

were

This

of these otherwise

technique also

platinum

Fluorescence

provided rather

from

porphyrin

[721].

in the Raman

found.

This method

directly

to the

of

allowed

the

protonated of

complexes

energetic8

a facile

intractable

the

first

[Pd(TPP)] and [Pd(Pc)] was studied

method

to obtain

complexes

and

second

in various

observation from

molecules)

2,9(10),16(17).23(24)-

tetrakis(4-(l-phenyl)-l-rethylethylethyl)phenoxy)phthalocyanines with fragmentation.

and

of the "R,

confirmed

of the a-band

in

obtained

Phosphorescence

obtained.

geometry

complexes were

17221.

spectrometric

mass

molecular

palladium

4.2 K

77 K were

the

porphyrin

polyethylenebutyral

core size and the wavelength

of palladium

of the porphyrfn

of palladium of

at

at 1.3 K and

spectra

of

final

solvents

in a glass

Correlations

The

of its

(7191.

selective

state

for

a

of the triplets

solution

structure

different

by a series

effect

parameters

aqueous

porphyrins

followed

in all cases was

using

a strong

with

palladium

and

diners

studied

field splitting

neutral

of

electron

palladium(I1)

consistent

solvated

N-methyl

the final product

formation

by

were

equilibria,

of

odd

dealkylation

N-methyl-5.10.15.20-tetraphenylporphyrin dmf

and

led to a decrease

the

to

[715]. for

data

that

used

derivatives

tetrakis(4-hydroxo-3.5-bis(l,l-d~methylethyl)phenyl)porphyrin palladium

cations

little or no

the molecular

weights

[723]. excited

solvents

singlet

[724].

states

of

101 association

syntheses,

The

monomolecular other

metal)

in

formation

layer

of

complexes

of

association

It

tetraner.

was

monolayers

for

in

excited

a

larger

Shpol'skii

singlet

Teller

been

which per

(and

various

substituted reported.

platinum

area

has

1.6.4.5

been

oxazepam.

complex, showed

with

The which

a

highest formed

high

phthalocyanine

K

donor

(216).

a

degree

moiety

of

in

the

metal

characterised

at

4.2

site

The

lifted

effect

on

K.

of

spectra degenerate

67r2

cai'

three

formation

were states

by

a

different

and

obtained

CP

of

mixed

vibronic

the

stabilised solvent

progressions

of

[727].

ligands

have

The

phosphorescence

were

The

4.2

[ML2Xz].2Hr0

spectroscopy. transition

at

investigated

fminc

Complexes

triplet

C7261.

matrices

and

matrices

and

effect

Shpol'skii [Pd(Pc)]

a

the

complexes

fluorescence

Raman.

[Pd(Pc)]

Jahn

for

that

Langmuir-Blodgett

platinum

[726].

Resonance

first

gave

have

groups found

noted

also

association

was

and

and

phthalocyanines

of

4-(1-phenyl-1-•ethyIethyl)phenoxy degree

solution,

palladium

and

been

[WLb]Iz

synthesised

ligand

was

complex

of

(M = Pd and

invariably an

or

Pt.

X = Cl

characterised

coordinated

iminoaziridine.

by

via

Br)

IR. 'H

N(4)

(217).

or

has

nmr

17281. been

of

the

and

The

UV

first

prepared

and

[729].

Me

Ph

Ph

A? (217)

A

number

iaine the and

function

(219)

17311.

as

PdZ+

at

of

acted

ff.N-chelating

the

as

reacted was

least

one

of

the

interesting

a

tridentate

with

(220).

vis

ligands

the

imine

studied

two

nitrogen

radical donor

HL.

complex towards

to give

nitrogen

and

this

year

donor (218)

have

atoms. was

palladium

included For

example.

described in

an

[730].

[PdLCl][ClO,]

a crans-complex,

[PdLP],

In which

the

pyrrole

nitrogen

deprotonated

17321. Reaction

polymer was

the

preparation

coordination atom

of

of

through

17331.

of

[Pd(PhCN),CIz]

composition the

Another

inine chelate

with

{PdCl.(NiS nitrogen

(221).

L ) O.PS 1. atom

involving

and an

[Nibt],

Coordination the

imine

nitrile nitrogen

gave of in

a

Nip, a

was

coordination to

palladium

trans-arrangement (228)

and

its

102 isomer.

geometric portions donor

of

the

towards

prepared carbene

from

ligand

(Pd(acac)}

or

the

in

carbene

(222)

{PtCl,)

complex,

could

also

(222).

act

as

an

The

imino

N,N-chelate

[734].

I

4 -0

AN,

.:“-r- p-fNbh

,a

‘=t+

‘N/

/”-t (218)

(=a)

(220)

NC Ni

(221) R

/ c’/”

Ii\\ ,C-Me

'-hg

l

cLN

Ph3P

_-TI

I

I ,’

I R

Q



NY--Me

(222) 1.6.4.6

Nitro

KrIM(No,).l alloy

1.6.4.7

Nitrilc

coating

due

study. to

the

[Pd(PhCN),Cl,J

Pt)

baths

was

used

in platinum

or

platinum-palladium

17353.

ligands of

ctp-[Pt(MeCN),Clz]

The

platinum-chlorine

structure

diffraction short,

complexes

(M r: Pd and/or

electroless

The

in

(223)

low for

trans-influence other

aryl

of nitrile

was bonds the

determined (2.264

nitriles ligands

k)

[736]. including

by were

an

relatively

Exchange ((r#)

X-ray

of PhCN has

been

103 The related

described.

radical

complex was studied

by epr spectroscopy

[737].

CN (224) 1.6.4.8 The

Amides

nitrogen

examples

palladium also

related

atoms

(225).

amides only

H,Q.

are

rather

in ligands

acted

as

a

with

rarely

coordination

before

geometric

tetradentate

in

ligand

complexes

HN

Complexes

on

of

(225)

complexes

the quaternary

triazfnt

Diazint.

were

L.

was clarified

prepared

including

such

nitrogen

as

(229).

diffraction

chemistry

and

by IR and XPES measurements An

interaction

and the anionic displacement

tctraasadicnt

study.

of

The diazabutadiene

nitrogen effect

through

the

was observed [740].

ligands

of trans-[Pd(PPhS)(Me&N=CH-CH=NCMes)CIZ]

with the chain extended The

complexes

and could be termed an electron

The structure an X-ray

ylide

palladium

between

1.6.4.9

HZNNHCONHNHZ,

carbohydrazide.

containing

in the ylide

stoicheiometry

(227), [MLtXZ] (M = Pd or Pt. X = Cl or Br) and the IPdLClzl, (228) [739]. A novel factor contributing to the stability of

aminiride

o-bond

of

both

of (226) were

A

(225)

nitrogen

towards

atoms

and

constraints.

1738).

CA NH

CPdL,(C&,)]. N.O-chelate.

coordinated

metal

strong

in [MQ] [6361. The imide nitrogen

and platinum

deprofonated

Mz[PdL.].nHzo

ligands

of

are found usually

example,

POI-

and

acted

was determined

as a monodentate

by

ligand

[741].

arylazooximate

complexes

has

been

reviewed.

Both

cis-

104 and Lrens-platinum particular,

complexes

reaction

of

are known and stack in the solid state

(290).

with

Kp[PtC14]

gave

(LK). (231). which was fully characterised by X-ray diffraction.

loose

stack

conditions However, distortion

with

the

a

trans-isomer

rrens-[PdL,] towards

did

was not

tetrahedral

(B = AraP, PMeZPh. in which

platinum-platinum

distance

obtained stack

and

and

geometry

of

was

a

The

[7423. In

cis-isomer,

The structure

3.151 A.

also

showed

17433.

the

fully large

reaction

Under

is a basic

characterised. and

unexpected

of

[Pd(L)BCl]

PMePh, or PCy,) with an excess of B gave trans-[Pd(L)&Cl]

L was monodentate.

The equilibrium

between

the species

depended

on

the steric demand of B [744]

‘-‘z

WNH

ap’

x b

NHNH2

*H H2

H2

(227)

(228) +

0

“zN-+A.. R’

(229)

0 t

NOH *

N=NPh

I

Ph

(290) The

structure

pyridin-2-ylhydrazine Foraazans

have

I-

Ph

(231) of

the

complex

was elucidated been

used

as

(232)

of

%-pyridine-2-carbaldehyde

by X-ray dfffraction the

functional

groups

17453. of

chelating

ion

105 palladium(II)

exchangers: atoms

was

readily

coordinated

to

the

terminal

nitrogen

in (223) [746].

(222) (Reproduced

1.6.4.10

Bidcntate

Reaction

of

ni trogcn

with

underwent

cycloaetallation

diffraction. addition

triethylamine

The

followed

mechanism

phosphorus

with

Xt(PtCL3

Treatment

with permission

PNH.

gave

the

on heating for

by NH reductive

donor

<234),

from

[745])

ligunds

gave

trans-[Pt(PNH-P)zC1,].

cis-chelate.

[Pt(PNP-P,IV),]Clz, which by X-ray (225). characterised

yielding

formation elimination

of

(225)

involved

CH

oxidative

[747].

0

cx

NHCOPh

PPh2

Treatment

of

[Pt(cod)X,]

with

PhtP(CHZ 1 oNHez

gave

initially

a

106

conplex

in

yielded

which

the

[Pd(PPh,),(N,)2]

was

phosphorus

with Ph2PCH&H&N

Carbonylation shifted

ligand

[Pt{Ph,P(CHt)3NMet-N,P}{Ph*P(CR=~

of

(237)

to the right using

gave

gave

coordinated.

Reaction

[312]:

3NMe,-P}Cl]C1

with

A&

Reaction

of

(236) [SSS].

(238)

reversibly;

[BPh.] as counter

the

equlibrium

could

be

ion 17481. +

cl-

(237) Treatment complexes, MeOSO,F

of

(a)

Kz[PtC14]

gave a product

complex,

or

PdClp

(ZSlD). characterised methylated

was establlshed

(m),

with

[(PhzP)2N]Li

spectroscopically. on nitrogen.

gave

Reaction

The structure

by X-ray diffraction

the of

homoleptic


with

of the palladium

[749].

ph PAPPh2

2\

I/

r”\

[email protected]

(M = Pd)

CMtcod)C1,1

of

Reaction

cfs.cfs.Crans-CPd,(~-(2-Ph,P),py),Cl,j. with

respect

with

M-Pt

to a

conversion camp lex

to

mixture

(are).

other was

isomers obtained

with was

which or

(241)

to

rather

gave stable

polymer.

However.

the

complexes

including

107

cfs.cis-CPt~(W(2-Ph*P)*py)*cl~l, (244). both solubility

of which was

were

important

and

(54519

identified

trens-CPtz{~-(2-Ph,P),py),1411

by X-ray

in determining

diffraction.

which

complex

was

It is ciear actually

that

isolated

[7503.

(240) (Reproduced

with permission

from E7493) Cl

I

PPh2 -Pd-Ph2P

I

0

Cl

N 3

Ph2 P C+F’h2Pwm2P-~-Cl

PPh2

(242)

(241) Trans-I(Pt(PEts)C1~)21. rPt(P~t,),L,IC~,7 alcohol

N(5).

Loss

diffraction.

of In

on an

when reacted

which

of the

PPh2

reacted with

intermediate

chlororethane similar

in

gave

reactions

with

to give

which

(245) was

(247). of

(245).

rethanol

the

attack via

coordinated

characterised related

yielded

L. (245) by

ligand.

by

X-ray

(248),

an

108

M

=

Pt.

Reaction

was

trans-[W(~)(PEtS)C1*]

intermediate (248) with

was

F-bonded, methanol

but

again

for gave

M = Pd ring

initially

produced.

N-coordination opening,

this

[751].

(243)

(Reproduced

with

permission

from

[750])

(244)

(Reproduced

with

permission

from

[750])

was time

For

dorinant. to

(249)

109

Me0

Me-

(UT)

(Reproduced

with

permision

from

(249)

(218) 1.6.4.11

Pure

Bidentate

nitrogen

carbon

donor

ligands

cio-[bls(2-phenylpyridine)platinnm(II)

trans-[Pt(SEt,),Cl,]. bow-like

distortions

[751])

The of

X-ray

the

diffraction

ligands

and

was study

a solid

prepared of

state

the

from

compound

association

(250)

and

revealed in dlmers.

110 with

the

Pt-Pt

significant

one

in

electron

material

irradiation

However,

k.

at

oxidation

showed

-1.94

(at

a very

there

Cyclic

solution.

reduction

but

transformation.

crystalline UV

3.53

association

reversible anion

distance

not

voltammetry V

involving

+9.46

strong

did

V)

was

emission

seem

to

be

revealed

an

almost

a

ligand

to

irreversible

at

room

any

radical

[752].

temperature

The under

17531.

(250) The

Electrophilic cleavage gave

and

protonation

involved

attack

of a

the

methylation

bond

N-C

2,6-dicbforopyridine

the

only 17541.

dimer,

cyclometallated

derivatives

[1cs1)

of

(253) been

been

2-pyridyl

Treatment

have

has

of

[234]. studied

investigated. without

nitrogen, (252)

wlth

Other

Ag[ClO+]

cycloretallated

[755].

$2pdbPtl 0

psp\w X'

AX

3

80

(252)

(251)

P

C1

0

Ph3P \

Pd

yo’

The checked

optical by

purity

A'-oxazoline-5-one

was It

I-phenylethylamine. active

catalyst

characterised

of

new

corplexation

[7571.

17581.

chiral

as studied was

Chiral

Asymmetric

2

binaphthyl

(=I

C7561.

using

concluded

2

a that

complexes, bidentate

biphosphine

ligands

system (255) (256), ligands,

formed was

from

the

have (257)

has

been

reduction

Enantioselective

PdClt/chiral

precursor been

of

of

prepared

(E = P or

As)

the and

could

111 be

resolved

complexes with

by

of

trans

Stereoselective

to

dIastereomeric

palladiua(IT)

forration of a chiral centre in (258) has been studied base when reacting

nar spectra

[762].

[7603.

the ligand with L& [PdCL]

[761].

have been recorded

or Br. R = OMe or Ii). No quadrupolar observed

of

I-phenylethylamine. Only the complexes [759]. were obtained arsenic phosphorus or

of an appropriate

proved important

"C

crystallisation

cycfolretallated chiral

nitrogen

The selection

fractional

for

(259) (L = PPhs or AsPha. X = Cl due to coupling to "'aPd was

broadening

112 Exchange been

one

studied.

The

but

also

exchange, such

of

as

cyclonetallated reaction

was

as

to

route

I-diethylaninoaethyl

directly,

but

would

conformation

was

cyclometallation

ligand useful

the

for

not

only

exchange

as

cyclopalladatlon

nitrobenzene.

was

important

(reaction an

of

which

It

[763].

extremely

another

of

reluctant

would also

in

(27))

example

not

has

ligand

substrates

cycloretallate

shown

that

determining

solution ease

the

of

1764).

CH

C

(27)

N

The

preparation

(260) * with described.

of

a

wide

range

{us-(PhrPCHCOOEt)) The

structure

of

and (261)

c

bridged

complexes,

cyclometallated

{(u~-Mo(CO),C~)(U~-C~)}

was

c\

of

determined

by X-ray

ligands dipfraction

has

been

17653.

/XLPd,C

N/Pd\y,

lN

>

(260) Cf141

c:15/

(261)

(Reproduced

Structure

Reaction R'COCI

(264)

formed

bridge

on

4

C(f2J

C(391 01401 I _.

Cllll

permission

from

17653)

with

(262)

gave

(263).

which

could

be

reacted

with

17661. of

(265)

occurred

with

3-butene-2-one.

treatment

splitting

with

C(131

[{Pd(6-mq)}sF~s-Mo(CC)=Cp~(~~-Cl)][BF~]

of Li2[PdC14]

to give

Cycloaetallation was

of

sP=-ta)

reactions

17671.

regiospecifically (266)

also

giving

(266).

underwent

the

(267) usual

113

(2631 R’ =H

(262)

R2 = Me

or

Me

1

or CH2COOEt

R3COCI

0 R

3

K[CN 1 <

AR Me:xz$

2

‘Me

Me

fdCl)2

[26&l

Me (265)

(266)

(267)

Reaction Treatment

of

with

(268) phenyl

with

[WCi,Jf-

ethene,

gave

however,

the

did

expected

not

give

derivatives. an

obvious

tm). insertion

114 but

product, suggested

more

that

unusually,

this

was

(270)

a complex

A

17681.

process

kinetic

(Scheme

study

5)

of

the

reaction

f769].

2

(289)

(268)

(270) Reaction and

a

of

number

(271) of

with

related

cyclometallated

diiaine

depolymerlsation

bridge

and

ligands.

the

[Pd(dba),]

gave

the

processes

were

also

polymer,

products

reactions

were

described

underwent

(273).

splitting

cycloretallated

on

characterised

diner [770].

in

greater

The

bis

the

expected

with

phosphine

all

treatment

(272).

detail

this

year

(7711. Further of

cyclometallated

azoarenep

4.4'-diaethoxyazobenzene

with

K2[PdC1,].

characterised

in

(275)

usual

by

appears

bridge

noted,

giving

(275)

the

190

adducts

with

Some and give

to

have

'C

and

pyridine

with

free

of

a

the

was

smectic

unusual

reactions

of

[Bu4N][CN]

(277).

a

but

conventional using

dppe

as

incoming

were phase

(278) bridge the

had

to

be

Reaction

on

reaction

give

(274).

therrotropic azobenzene the

netallation; quinoline

trans

new

to

were

carbon.

neaatic

In

aesophase

measurements. mononuclear

The liquid

[773].

have and

a

and

fluid

present

splitting the

was

and

shown was

aniline

miscibility

(X = OCOMe)

ligand

to

non-symmetric

ligand

by

year.

dimer

regioselective

birefringent

quinoline

a layered

The

pyridine,

confirmed

in which

this

bridged

complex

17721.

rather

strongly

'C

and

Neither

with

in which

205

prepared

8-hydroxyquinoline

ligand

undergone

reactions

complexes

been

a cyclonetallated

diffraction. to the

splitting

existence

between

crystals

X-ray

in contrast

mesophase.

gave reacted

This

have

been

noted.

substitution

With

PPh,

occurred

3-aminobenzo[g]indazole,

to

(2781,

115

was

f orned.

with

Reaction

CyNC

the

gave

insertion

product,

(299).

for

X = OCOMe but the more conventional bridge split complex, (-1, without PPb and when X = Cl 17741. When (281) was treated with [PdC1h]z- retallation occurred regiospecifically at the aryl ring. (282) was then converted to (283). which on attempted retaliation

([email protected]) possibly vir

gave

(285)

and (286)

17753.

>

SF 0

NMe2

Scheme

of

5 Mechanism

phenyl

ethene

insertion

into a cycloretallated

C7691

Me0

Me0

EtUdbdJ Me0

Br

-

Me0

R

direr

116

H

Hi61

(294)

with

(Reproduced

0~0

permission

wi2)5Me

1

0 0

N#\

b 0

,x

w

P

2

AEt

(275)

from

[772])

117

[ Bu4N l[CNI , PPh3

(276)

,\m4NIICN

Metallation

of

usual

bridge

derivative synthesis

complex with

as doubly was

yield

(2QS).

charged,

occurred

was

an

also

has gave

(2Q7).

17761. early

transition

which

for

been

noted.

which

was

in a rather

Reaction

subjected

Cyclometallation

step

of the

When

(293) be

to

of

reacted

observed.

The to

kinetic (292)

the A

analogous was

A

give

[779].

retallatlon

(290).

I assume

(291).

attack state

in which

to give

lnitlally

nucleophlllc

could

reactions

(222)

amlnes

described

reaction

rings

L1,JPdCl.J

of novel

a

of

to the

ferrocene

prostaglandln

17773.

The reacted

with

splitting

to

CN

1

5-membered

2-(I-pyrrolyl)pyrldlne

00 cb

F

platinum with

study and

via

complex

a

the

bridge

controlling curious

invoked

to

group.

describes

(QQQ)

reaction splitting step

was

four-membered

explain

the

same

[78OJ.

in ethanolc

spectroscopically.

a rethyl

A related

that

rate

rather was

on paper

17781.

suggested

that

mechanism

LlCl

occurred of this

be a misprint

amine

similar

had

abstract

acid

Therrolysls

the

intermediate

gave

PhCH,NRZ

(a) and

119

+ kNHR

-

NRR’

1

(291)

ArNH2

0

L2W \ 33

(

k~Ar

F;Ph3

rn3

I

w -Cl 1 N-R

LiCl, 25’

B

MeCOOH

exchange [782].

+

I( ffl (PPh3)Cl2)2 I

t-1

t-1 rather

PhCH2NR2

HNR t 2

I R

A

A

unusual

reaction

of

ray

to prepare

(295).

Bpr

cyclometallated

reasurements

were

complexes performed

is the on

the

metal

product

120

X

0

BrM----tj

In

(2S8)

strong

(M = Ni

evidence

orbitals

P%P

or

for

a

Pt,

X = Cl,

w-interaction

phosphinc

Unidcntrtc

rrans-[Pd(PPhs),Clp]

was

used

including

reacted

to

structure

and

used

make

cis-[ML&l,] of

I; M = Pd, the

x = Br)

phenyl

ring

UVPES with

provided the

metal

a

number

was

(M = Pd

in derivations

with

of

or

4-chloro-2-butanone

of or

of bond

by

simple

Pt),

and

by

enthalpies

Pt.

X-ray

heterobimetallic

R = Et,

energies

X-ray of

Cy,

to

or

[784]. complexes

and

(BSB),

diffraction

decomposition Ph

give

diffraction

cis-[Pt(TiL,Clz}Clz]

determined

measurements

[M(PRB)aC1z]

ligsnds

characterised

(M = Pd

which

Microcalorimetric as

of

donor

[Ph~PCH,CH&OCHp][Pd(PPhS)C1,l.

such

or

[783].

1.6.4.12

(297)

Br

of

CIiMe2) have

the

[785]. complexes been

made

[786].

(297)

The

He I and

assignments were

studied

were as

He made a

II

PES

[787]. function

of

trans-[Pd(PEtS)zXt]

The of

nmr the

spectra varying

of cfs-

have and

electronic

been

recorded.

bans-[Pt(PAr3

character

Some )tCq

of

]

Al‘.

121 'J(Pt-P)

was

isomers

and

[788].

The

found could

to

be

also

an

be correlated

trsns-effect

fPtfPEt,frCIXI reasonable

was

of

studied

agreement

unambiguous

with

&&n-Teller

(X = H,

In

experintent.

the

triplet

with

singlet

with ~cO.1

the rrans+eis The

usec

process

of

electron

associated products

with

was

autoinhibition

of

of

the

by

a

gave

reaction

reaction

has

PPh=,

in

the with

a

long

lived

short

lived

suppressed

cis-

of

been

Au a

and

intermediate, report

of

X = C1 or

an

[CNS])

from zero to -0.35 V.

complexes

electrode

of well

[790].

P(OPhjS.

in dmf ranged the

were

a

quenchers

voltauetry.

There

potentials

agree

equilibration

(L = PBu3,

reduction

analysis to

of triplet

cyclic

[7913.

JPdLzXz]

reversible

using

data

for

to

process

palladium(Q) by

was

electrolysis

1?92,?93].

[Pt(PPhs)&l,] PhJPO

studied

the

found

cfa+trsns

Addition

groups

moments

f7851)

photoexcitation

the

catalysed

Redox

[Pd(P~CR~(PPh=}Cl=J.

two

formed.

identified

was study

in

was

to the level of the reverse

was

IPt(PPhs)sCll.

was

Identified

prepared as

ligand and as a reducing and

was

trlphenylphosphfne

electrochemical and

process

whereas

7310 @sec.

rran~-~Pt(PPhJ)&lz]

A

rruns+cfs

from

for

used

aryl

the

[789].

with peraisston

and

dipole

Experimental

Ph).

predictions

[Pt(PEtb)ECfl]

distinguishing for the

calculated

or

was

theory

of

for

the o values

on

Me

theoretical

effect

photoisonerfsatfon

with

lfgands

(298) (Reproduced

criterion

a

by-product

agent

CPt
new

method

implying

from that

[794]. The complexes were

prepared,

KzCPtCls]

PPha

acted

and both

PPhg. as

a

[Pd{P(CH*CH,CN]9},(SCN),] indicating

that

linkage

122

isomerism

is

very

sensitive

trans-[M(PhZPCHzSPh-P)zClz] species

to

(M = Pd

steric or

Pt)

effects with

HgClz

[795]. gave

Reaction the

of

bimetallic

(299) [796].

The synthesis and transforrations detail (Scheme

of [Pt(PEt9)3C1]+ have been explored

in

6) 1797). base

IPt(PEt,),(SO4)1

T

Ag,

[Ptz(OHz)(PEts)~~=+

II+

/

[SO, I

Aa [SO+1

Hz ISO4 1

CPt(P~ts)s(oClo,)l+

/ cfr-[Pt(PEts)zCIZ] Rh

[Pt(PEt9)4]*+

1;;:;;:;

-

[Pt(PEt~)&11+

CPt(PEts)J[PtCLl’

of

possible

phosphine

CPt(PEtS)s(OHa)]=+

cis-

and reactions of [Pt(PEtS)sC1]+ or

trana-[Pt(PPhS)zIz]

gave cir-[Pt(PPh9)2(B,oHIo)l two

z

[Pt(PEt,),(OCOHe)]+

Scheme 6 Preparation Reaction

U~YpEts)~[C;~;;;

structures

and

(SOOa)

o-HCBIOHloCCHtPPh,

with Mt[Bl,,H,,,]

[HPt(PPh,),I]. and

forred

(SOOb)

17971 (M = K

Spectroscopic

with

conventional

Pt-H-B

Ag)

data suggested

bonds

corplexes

or

[798].

erarts-[ti2C12]

The

123

with

(M = Pd

[MCl,]*-

or

Theraolysis

Pt).

ring q etallocycle,

give a flve-membered

resulted

in cyclometallatlon

to

(301) [799].

(390) (Reproduced with permission

from [798])

Probable structures of the complex cis-[Pt(PPhS)t(Bl,JiIO)]

;M=

(301) (Reproduced with permission

Cis-[Pt(PPh,),Cl,] to

give

a

series

catalytically

reacted with alkynes

of

on

o-alkynyl

photolysis

gave

palladium

complex

decomposing

initially to

Other

HBr

and

was hydrogen

was

a

unfdcntatt

[Me,NR,J[Pd(P(OPh),)Br,l containing

(302)

an acid.

which

Hydrogen

aqueous Kinetic radical.

also

LiBr. bonded

'deterrined

phosphorus

donor

was prepared An

X-ray

from PdBr,

diffraction

diffraction

an electron [HPd(PR,),]*

Platinum(lI)

Treatment

phosphite

complexes

were

and P(OPh)S

study

that

to the .

this

[801].

formed

indicated

in butanol that

[SOZ]. The structure

techniques:

wldened to 97 ., presumably due to steric crowdlng

in reactions

of

implied

lfgands

to an NH of the cation by

solution produced

solution

studies

transferred

palladiua(f)

was

rapidly in protic solution to yield molecular hydrogen

1.6.4.X-3

bromine

of

[Ru(bipy)J]+

from [799])

[SOO].

and ascorbic

give

Pt

in 30 X aqueous ammonia

complexes

photolysis

[HPd(PEt,),]+/[Ru(blpy)S]*+

Pd,

the

P&F

angle

the of was

[803). from platinur(9)

coaplexes

(28) and (29) [804J. of [Pt(P(OMe),)zCII]

with Na[RH,J gave tran~-[HPt{P(one),),Cl],

124 which

was

stable

Both

inserted

in

methyl

propenoate

cis-[PtL,{CH(CH,)COOMe)Cl] reacted Variation reacted with

with of with

[liPt{MeP(OMe),),Cl]

solution.

readily

[805].

the

aryl

group

ArCHzOPFz

caused

to give

to

give

no

change

(302)

(303)

which

in the

with

in most

was

permission

formed

from

to

give

ArCH,OPF,.

eliminated

reaction.

[ArCH,PPh,][Pt(POPz)a]

(Reproduced

similarly.

regiospecifically

and

trans-[Pt(POF,)(PPhS),C1]

4-MeOC,H,CH,OPFZ,

prepared

alkyldifluorophosphite,

An

trams-[Pt(PEt,),Cl,]

waa

ArCH,Cl.

[Pt(PPh3)zC1z] cases.

However,

f8063.

[SOS])

HCl

IPttPtOEt),),l

+ 02 -

CPt~PIOEt)~~~l

+ 02 -

CPt{P(oH)[oEt),),(P(o)(OEt)t)t3

(28)

H[CIO,I cPt~P(oet),~~l'+

Pa3 +: I f ArCH20 -P -Pt*11 c

Cl

(29)

;r w

0-P

PEt3 I -Pt-Ct

t

Ar CH Cl 2

’ PES (303)

A mixed [807].

(-41

cis-[PtLpClz]

metal

complex

acted

as

with

bridging

a

phosphorus

llgands donor

was

formed

tonarde

in

reaction

platinur(I1)

(30) irk

[808].

2[(OC),Mo(PhtPOPPhz)]

+ [Pd(PhCN)&l,]

----+tranr-~Pd((PhtPOPPhz)Wo(CO)5)2C12] (30)

126 1.6.4.14

Bldcntatc

Solution

absorption

[M(dppe)z]Xz phosphine

and

(M = Pd,

and

phosphorus

multidentate

and Pt

phosphite

CD

magnetic

or

spectra

X = [PF=]

Ni.

Each

complexes.

or

coupling

ligands

have

been

[ClO,])

as

showed

complex

assigned to metal to iigand CT bands. Detailed of a model including spin-orbit

donor

reported well

several

assignaents

for

as

other

W

bands

were made in term

in excited WLCT states [809].

(304)

The

has

cis-chelating R=NMe,.

behaviour

dynamic

[Pd(diop)Clz],

been and

gave

(305). characterised

benzonitrlle

of

by X-ray diffractIon.

with

Addition

diffractlon.

In all the complexes [812].

dynamic

Reaction of (308) (R = CMe,) with X-ray diffraction.

or

or

behaviour

P

or

R = NMe2.

by 'Ii. "P

and "P

PhzPCHzP(Ph)CHrPPhz of an excess of the [PdsL2Cl.]. probably

was observed

by X-ray 'lP nrr

by

[Pe*(CO),] gave (399). characterised

by

With R = Ph. Cy or SiMe,. however, (STO) was formed [8i3].

of (511) with

[CpPd(n'-Co&)]

to give (313). characterised Phosphinated

NMe,

(305). (307) was also prepared and characterised

spectroscopy

The

[810].

(R = R' = CaFs

[Pd(PhCN)&l,]

including

diop.

(R = R' = Ph.

complex yielded a species of stofcheioxetry

with the structure.

Treatment

of

spectroscopy

[PtLClz]. These were characterised

[Sll]. Reaction

spectroscopy

nmr

(HetN)*P(BloHloCt)PRR'

R' = P), gave complexes nrr

complexes by

PhzP(B,OH,OCp)PRR'

ligands.

R'=P)

aetal

of

ivestigated

polymers

gave

(312) which reacted with iodine

by X-ray diffraction of

the

type

[Sl4].

(314)

reacted

with

readily

IPd PhCN)2C12] to give 1:l and 1~2 complexes [SlS]. been converted to has c~Pt(~-dmPx)Cl,),] CPt(SMet)tC121

and

to

CPt dspm)Clz] as well as to various o-alkyl coaplexes (drpm = MezPCH+PMez) but the paper describing these reactions is rather irritating in that it does not give

details

Li[N(SiMeS)zJ details

of

this

[Mn(CO),X] with by

X-ray

of the reagents

followed

by RX gave

process

[Pd(dba),]

diffraction

for

interaction with palladium

have

used

[815]. Reaction

[Pt(Ph,PCHRPPhr)Xz]. nor

been

in the presence X = Br. [Sl8].

Two

of

of

published of dppm gave the

[Pt(dppr)&

] with

and full experimental

carbonyl

I817].

Treatment

of

(315). characteriaed groups

shared

some

126

(305) (Reproduced with permission from [812])

2Ph

3-Pdc12

(c’zpdLP

Ph2

(307) (Reproduced with perriseion from [812])

Treatment C{PtWhPCCH,) adopted

of

sPCy,Clltl. X-ray

square

planar

chair conformation. both had unit

were fully a planar

diffraction

coordination

The diastereomers

characterised

(M2P,)

core

but

and

the

indicated

had

diffraction. a bent

that

six-membered

(Sl6) and (Sl7) could

by X-ray (Sl6)

studies

that

gave

IStaN

platinum

rings

had

be separated.

The stro-complex,

arrangement

for

the

a and

(Sl7) (PtzPz)

[819,820], The

chelating

unsymmetrical

RLPICHp)3P(Ph)(CHL)nPR'L, were

with

CPttpb(H)P(CH,)spCY,),C1,1

synthesised

rapidly

of a second

phosphfne

(31)).

resulting

The

triphosphine

ligands

(R = R* = Ph or Cy or R = Cy. R' = Ph. n = 1 or R) on platinum

unit

with

by triethylauine

a coordinated

[Pt(triphos)Cl]Cl

catalysed

secondary

complexes

were

condensation

phosphine

(reaction

characterised

by

128 microanalysis. phosphines

IH.

3lP

*ssPt

and

were also synthesised

spectroscopy

nmr

in a metal

[821].

coordination

sphere via reaction

(32) (M = Ni, Pd. Pt or Zn: X = Cl or Br; R' = H or Me; @ 3;

n = 2

or

3).

Careful

diastereoselectivity

of

analysis the

of

reaction,

nm

spectroscopic

which

was

Tetradentate

m = 2 or

= GE&; data

generally

revealed

better

the

for

the

formation of the small ring complexes.

b

01

(513) (Reproduced with permission

from [814])

(314) Assignment (K,[Ptz(pop),]) coupling.

the

of

was achieved

All the absorption

transitions

except

transition.

The phosphorscence

which

is mainly

was emission using

on the basis bands

below

composed

states

43.000 CC'

were

KIIPt*(P*CsR* 141 of the spin-orbit assigned

at 32,500 cm-' asigned

observed was @mission

of the

of

of calculations

for a weak absorption

'AzU zero order

data

from

assignments linear

of the excited

polarization

to 5d+f3p

to a 5d+5d

from the lowest 5

state,

whilst

from the lowest Azu state mainly composed of the '&u

state [823]. Symmetry made

electronic

lower

state

fluorescence zero order

states of [P& (pop)*]'- were

ratios

[824].

The

influence

of

129 magnetic

fields

crystals

has been reported.

4 Tesla,

the

280 cm-'.

on

low

and

at

emitting

soz

triplet

a

from

"P

as

When

the magnetic

(TC4.2 K)

striking

excited

Ku

change

and

The

from the electronic

Pt(I1)

field was raised

of the

phosphorescence by addition

sites

was

emission of sulphur

binding

was

from [818])

(3171

intensity dioxide. supported

constant

Ring 7

(313)

structure

of the complex.

[826].

(315) (Reproduced wlth perrission

fror zero to by was The

as 'Azu and that of the

in an n' -manner The

single

blue-shifted

vibrational

confirmed

spectroscopy. spectra

Baz[Ptz(pop),]

within the symmetry

was quenched

Ranan

of

phosphorescence

state was

[SZS].

at the axial nmr

phosphorescence

could be explained

[Pta(pop),14-

coordinated

estimated

10 K

of the lowest

517 na from data

polarized

temperature

noted. The results symmetry

the

could

at That by be

130

r-lP---H php\

Et3N

/Ph

+

-PPh2

-

PV,

Pt’

C;’

n

jPh

rn>

+ ,P Cl-

\I

>

CIApt\P

Phi!

MeHP(CH&,PHMe >

OH \ A, (CH21m A_/

The electroluminescence triplet

excited

amine quenchers

state

was

including

of [Ptt(pop),)*reduced

to

f-f

/ ,P\

(32)

has been Investigated

[Ptz(pop),]s-

by a series

1,4-bis(dimethylamino)benzene.

[S273. Its of aromatic

suggesting

that

the

132 occurred with phosphines and the products could be reacted with SnClz to give (322)

(L = Ph=As.

were reported

PhsSb,

CO.

PhrPMe

or PCy,).

18333. However, with the pyrazole

Many

nnr

spectroscopic

data

as addend, bridge splitting

did not occur and the new bridged complex (siw) was formed [834].

(919) (Reproduced with perriseion from [331])

133

(525) (Reproduced with permission carbons of the non q etallated

(The methyl

from [834])

CMe j groups are omitted

for

clarity) cisand/or with C&XX gave CPt(PPha)z(C,R,)l trans-[Pt(PPh,)p(CH,X')X] (X = X' = I. X = Br, X' = Cl or X = I X' = Cl). In Treatment

the presence give

of

of Ag[BF.]

(S24). Without

S. (325) was formed.

the trans-isomers

reacted

It was considered

the initial step in the reaction

Na[BH,]

to give

(326)

for M = platinum

treatment

with

that the breaking

cis- and were prepared

in propanone

[HCOO]Na yielded

1.6.4.17 Arsenic

donor

trans-isomers by reactions

were shown to be dimeric

benzene

(X = halogen).

to

ing solvent,

of the M-X

reacted

with

X may be replaced

but with W = palladium

Ag[CPISO,]

with

coordina

bond was

(325)

1.3-Bis(diphenylphosphino)methyl

Reaction

triphenylphosphine

[835],

(324)

platinum(I1)

with

added PPh, and in an appropriately

gave

decomposition

(326)

palladium(I1)

using

occurred

ISSS].

(X = propanone),

(521). which was surprisingly

or

by hydride

stable

which

on

[837].

ligands of

[PtLCl,]

(33) and

(8381.

L = Ph,As(CR,),&sPhl

(n = 6-12

or 16)

(34). For n = 10 or 12 the cis-complexes

134

-bPh2 (327)

(2261

propanone/toluene K[Pt(CpHa)C13]

+

+ L

(33)

a/ethanol K2[PtC14]

+

-

L

I-6.5 Complexes

Many thus

cis-[{PtLC1*}t]

vich

Group

of the complexes

fall

outside

the

beginning

compounds,

scope

method

structure

of

combination

of valence

MO's

studied

preparation

as a function

deduce a value

of

14 donor

this

ligands

review.

The

history

related

was

complex

of

proposed

for

molecules.

[Pdz(CO)zCl~]

of temperature

the

It

of the fragments,

of 101 kJ mol-'

oxidation

nickel

fact may

state

PdClz

and CO pressure.

for the Pd-CO

complexes,

to explain

(35) for the related

palladium

cPt*( CO),(U-C~)~C~,]

+ 2C0 -

i-6.5.2 Cyanide The Kt[M(CN),]

and

organometallic

18391.

the

fact

complex

based tested and

largely

the

on

CO

a

linear

SOClz

were

Pd(II)-CO a

with

than

is no analogue

was

in

the

those

of

to the

bond

due to poor back bonding.

there

was

used

decrease

is weaker

the

[Pt(CO)Cl,]-

in

Comparison

with

bond

of

on

The data

bond energy.

this

that

calculation

was

and was

from

[841]. However,

and platinum

be used

of

salt, has been discussed

species. [Pdr(CO)pClr]z-. suggested that Pd(I) "normal" in strength and that bonding decreased palladium

are organometallics

complexes

semi-empirical

The

ligands

of Group

electronic

[840].

donor

with Zeise's

1.6.5.1 Carbonyl A

X4

(34)

in

This

reaction

18423. fast + cis-fPt(CO)rClr]

2trano-[Pt(CO)zCln]

(351

complexes

complexes

[Ph,I],[M(CN),]

and PhzICl

(M = Pd

1843). The species

also synthesised

[844]. Reaction

[Pt(dien)(CN)l+,

[Pt(dfen)(CN)t]

Pt)

were

[R,S]+[Pd(CN),]

of [CN]- with and

or

The

from

(R = Me or Ph) were

[Pt(dien)X]+

[Pt(CN)&]'-.

prepared

NH

gave group

successively of

the

dien

135 was the first ligating The

effects

single

of magnetic

crystals

generalised

species

at

1.9 K

partitioning

electronic

states

to be replaced

fields have

A

study

of

of iodide

the

revealed

give

to

the

unique

diner

units.

desiccator

substitution

related

en

complexes

solid

by

activated by water

escapes.

[M(CN).]'-

which

the

Places

[CNr

to

give

than that

was

platinum

Pd

or

Pt)

was formed

by

Pd

DSC

derived

complex,

which

elimination.

the rate of the reaction

and

or

an

SNl

explained

slips

depending

some

stand

in

anation

a

and

give

non-isothermal

process

in terms

of

to

Pt)

isothermal

implied

was

Water

As

18491. When

to

deaquation

(M = Ni.

studied

data

showed

interactions allowed

or

groups.

cyan0

derivative

was

Pd

[850].

thermal

energies

(M = Ni.

spectroscopic

IR bridging

platinum-platinum

M = Ni.

phase

activation

pyramidal

via

a

square

of Prenkel

defect

into an interstitial

position

on the size of the holes

and

in the

[851].

The

new

complexes.

and

prepared

determined.

the

that

attributed

to

Reaction

of

first order complexes

solid

sate

l-6.5.3

and

process

Xsonitrilc

aryl

reaction with

to give

association the water

with

for

in

the

molecules

Pt)

were

anation

was substantially

the difference crystal

to escape

cis-[Pt(CzH4)(4-Mepy)C12]

1~1 and 2:l species.

or

deaquation

complex

analogues.

Pd

lattice readily

which [852].

occurred

A range of related

being

by

a

bridging

[853].

caplcxcs

isonitriles. [Pt(cod)Cl,]

complexes from

or palladium

allowed

investigated

parameters

for the platinur

platinum-platinum

[Ru(bipy),(CN),]

were

kinetic

energy

for the nickel

distortion

(M = Ni.

[Co(H,O)(NH,),],[n(CN)~]~

The activation

lower than

prepared

calculate

[CN]- was weaker

with and

the

[(en)rXCr-(NC)-M(CN),1

formation

The

[Pt(&O)Isl-

of the

terminal

of

involving

[(en)2FCr-NmC-M(CN)S]

The

of

reacted

rrsns-[CrP(H,O)(en),][M(CN),I

caused

to

The mechanism

cfs-[(1.2-pn)ZPCr-(NC)-M(CN)SI.Ht0. presence

The

lattice

multiple-scattering

[847].

ligand

the

behaviour.

The

A

used

level in the I& [Pt(CN), ] quasi one-dimensional

that the trans-effect

cfs-[CrX(H20)(en),][M(CN)~]

TG.

of Ln,[Pt(CN).]3.Hz0

(8461. was

18451.

[848].

established with

studied

model

~rans-[Cr(HpO)(l.2-pn)zF][C10.J Pt)

luminescence

cluster

of the [Pt(CN),]'-

solid was analysed

CPt(CN),l'-

been

molecular

the dZ2 like band at the Fermi conducting

on the

by the cyanide

(328),

formed

simple

complexes.

cis-[PtLtC12],

on

1854.8551.

trms-[Pt(PPh,)pLC1]Cl

cfb-[Pt(PPh,)rC12]

(L - CmN-C(R)-C(R')-NR",)

and L. Thermolysis

gave

were

cis-[Pt(PPh,)LCl,].

136

The

isonitrile

derivatives

complexes

reacted

readily

K Reaction bromide

amines

to give

diarinocarbene

X

0

A

with

[8563.

of dmb.

or

(329) with Pd(II)

chloride

[Pdz(dab),X]"+

ion could

C

in protic

solvents

be encapsulated

between

gave

[PC& (drb), r’

the metal

atoms

.

in

[857].

(329) Treatment

of

reaction

Transfer

of RNC

from

gave

WeSCNC [Ag(CNR)Cl]

occurred

in

(38) (M = Pd or Pt) [858].

CM(dpw)zlClz

+ fAfz(CNRlCll

X.6.5.4 Silicon Reaction Tetraalkyl complex

with

CPt(dwm)C1zl

cis-[Ptz(~-dppa)Z(CNCMe~)~]4+.

of

donor

[(RNC)M(u-dppa),AgCl]Clz

a

reacted

catalyst

for

with

similarly siloxane

HSiPhzSiPhtSiPhpH to give

(331)

oligonerisatlon

[860].

Ph2

‘S’\ ASiPh /pl\si/ * Ph3P Ph,

t-1

(36)

ligands

[Pt(C,H,)(PPh,)Z]

disiloxanes

being

-

(391)

gave

(229)

18591.

(M = Pd or Pt), and

this

redistribution

137 1.6.5.5

Tin

donor

The reactions wide

range

of

lssSn and

[Ml].

complexes

importance

of

such

and

in the number

SnClo

gave

This was

ligands which cause

the

initial

labilised species

product

the

was

phosphole

in solution

in contrast

solution

red

18651.

CPd(SnC19)41 '- fixed on AV-17-8

bond isonerisation

in

which

of

bright

in hexene

1:l.

on addition SnCIB groups

of lssPt. Reaction

of and

to the reactions

of Group

[SSZ]. An I" Sn Mbssbauer

study

[SSS].

towards

Treatment

discussed

for the range of

of coordinated

was reacted with SnCl,

[PtL,(solvent)(SnCl,)Cl]. complexes

(8641.

was

nmr

[Pt(SnC13)&l]*-,

(L = 1-alkyl-3,4-dimethylphosphole)

[PtL&l,]

a'P

CPtzLz(u-Cl)r(SnCIJ)Cl]

bridge splitting

of these species has also been reported When

catalysis reported

llsSn and the shielding

of

trans-[PtZLz(U-C1)Z(SnCl~)z].

in

and

which were formed successively

An increase

with

[(PtL(U-Cl)Cl),I

'lsSn

issPt.

data were

A

have been studied.

[Pt(SnCls)2C12]zc,

[Pt(SnCl,)sJ'-,

in the deshielding

by

species

lssPt MI‘ spectroscopic

of SnCl, to [PtCl,]=.

15 donor

with P(OPh)9

identified

[Pt(SnC1J)C19]z-.

[Pt(SnCl,),]'resulted

was

complexes

The

spectroscopy.

ligrnds

of cis-[Pt(SnCl,)zClzlz-

ligand

The

addition

exchange

[Pt(n'-C,&)Cl+]

1:2

and

1:5

with

SnCl,

several

SnCl,

were

complexes

anion exchange

of

yielding

gave

a

identified

resin catalysed

double

[SSS].

1.6.6 Hydride complexes A theoretical to give to

[H+Pt(PH,),]

66.8 kJ rol-', platinum

with

an

that the hydrogen

and

state

of [Pt(PHS),] with molecular

that

activation

the

energy

Concerted

additions using

complexes

22 kJ rol-'. cases.

The

increase

resulted

on

of hydrogen

basis

were

formed

ground

in

of

the wave

the

s’dS

bonding of

function.

diffraction

cases

with

and palladium

The

addition

and

of covalent

The

rdle

binding

palladium

of

the

favoured

an

[8681.

it was

found

energies

of

were different caused

hydrogen

of water

facilitated

by

atom and to {Pd(bO),

Whilst

atom

palladium

intact up

calculations

iniLf0

and geometries

the

configuration

rupture of the hydrogen-hydrogen A neutron

ab

hydrogen

exothermic

[867]. Other workers

CI calculations.

in both

state

in the formation

of

remained was

9.7 kJ mol-'.

to the naked palladium

rultireference

the equilibrium da0

the

in the H-H bond distance,

reflected energy

state

molecule

reaction

of

s'd' and d'O states was discussed

transition

were studied stable

suggested

transition

the

early

study of the reaction

sd

hydrogen

ligands

about

in the two

only

bonding

)

that

a

slight

was hardly lowered

hybridisatlon.

the This

bonds and the total

bond [869].

study of

[H,Ptt(dppe).][BPh,].

(35t).

allowed

the

location

accurate

and

coordinate

was

structure

Pt-H

other

that

the

sixteen

bonds

is

Two

views

of the

Despite protic gave

in

fragment

fact

core

that

the

reaction alkallne

from

were

donor

acceptor

a

of the

of other

this

complex

yielded

In

bridged

which

the

through

two

18701

18701) cation.

Only

the

trans-[HPt(PPh3)tC1]

fpro

is

not

trams-[Mo(N~)~(PM~P~~)J Hydrogen

photolysis.

ally1

unit

the

for clarity.

with

18711.

on with

shown.

atom

hydrolysis

readily

reagents,

are

hydrogen of

from

[H,Pt,(dppe),]+

rings

[HzPt(R2P(CHt),PR,}] reacted

permission

in

as a donor

(HPt(dppe))+

of

unsymmetrical

very

complex

acts

(HzPt(dppe)).

with

in

four

was

atom feature

noticeable

hydrides

electron

of the phenyl

after

produced

absence

(Reproduced

character,

ammonia

eliminated

the

the

fragment, fourteen

central

carbons

of

platinum

One A

coordinate.

bridging

electron

(Ssa)

five

suggestive

to a cationic

atoms.

hydrogen

the

the

This

positions. neutral

of

The

derivatives dirers

was

reductively

{Pt(hPtCHt or

[872].

alkenes,

hP& or,

11 In

139

1.7 PALLADIUM(I)

AND PLATINUM(I)

An excellent In a reduced Pd+

ions

and therroevacuated

were

increased

review of metal(I)-metal(I)

observed.

the

The reaction

palladium

Absorption

concentration of a glowing

dimers has been published on MgO catalyst

of oxygen

of Pd+

at

platinum

filament

epr signals

20 'C on reduced

as Oz radical

anions

[163].

were

with molecular

due to

samples

formed

bromine

[873].

at 1900 K

gave PtBr [lSO]. "P

and

J(Pt-Pt)

lgsPt nmr spectra

were

the coupling

strongly constants

give

that

probably

giving

the

rapid than

material insertion

metal-metal with

rate

bond

K[OH]

in

[Et,N)Cl

might

[876].

ethaonol

at lie

platinum-platinum

Pt(O)+Pt(Ii) distortion

donor

the

insertion

and of

[874].

S).

Kinetic

dissociative

[Pt,(w-dppm)2C1,]

the

of

more

explanation

was

of

of

for the

reacted

bis(diphenylphosphino)methanide.

could

also

much

rrans-effect

was

formed.

The

is not inconsistent

with a

(334).

this

would

reactlon. reaction

was

An

large

data

also

explain

be

the

described

observed

as

a

tetrahedral

[887].

carbonylation

A-frame

complex

occurred

unfavourable halide

which

or

platinum(I1).

in

derivative

However,

bond,

at Pt(l)

The reversible give

a

bond was 2.658(2) A long, which

formulation.

dependence

CPtt(pphs)t(u-dpp=)tIIPF,I,

When

the

CIi*, SO*

underwent

[Pt,tPPh,),(~-Ph,PCHPPh,)(~-dppm)ltPF~l, Pt(I)-Pt(I)

6(31P)

of L. Some

18751. The halide exchange

to- give

substitutions

related

accelerated

high temperature

(Y = CO,

starting

with

recorded.

character

reacted with species X (X = CO, CHzNz, SO2 or S,)

(333) before

CPtz(~-dppm),Srz]

were

by the *-acceptor

IPt,(PPh,)2(~-Y)(u-dppm)~]

implied

the

[P&(rr-SPR,),L,]

showed an unusually

[Pt~(PPh~)z(~-dppm)z]z+ to

of

influenced

L\s tera.

dissociation

(dmpm = MepPCW,PMe,).

of [Pd,(u-dppm),X,J

CPd2(u-dppm),(u-CO)Xz]

because

the

It appeared [878'J. prepared

(x = Cl, Br or [Nco]) to

The frOR

procees to

be

was

one-stage

related dmpa

was

amd

Investigated.

exothermfc. process,

complex, [{Pd(CO)Cl},]

despite not

CO an

involving

IPd,(w-dmp=),Clzl at

-78 'C. also

140 reacted

with

characterised with

CO

to

give

to

give

CO

species,

A-frame

by X-ray diffraction.

CPdz(u-drpm),(OPh)r]

bonds

an

was

[Pd2(p-dmpm)t(Ofl)2] reacted similarly inserted

into

species gave CO*. among other products

both

the

Therrolysis

CPd2(p-dmpm)z(~-CO)2(COPh)2].

Pd-Pd of

and

this

but

Pd-OPh

bis(acy1)

[879].

(3341 (Reproduced with permission A perspective

CPdt(~-dmpm),(u-CO)cl*],

from [8?7])

view of the metal coordination

polyhedra

in the

[Pt~(PPh3)2(Ph2PCIiPPh2)(PhzPCIizPPh~)]~ cation. For clarity each of the fourteen phenyl rings is represented

Isonitriles the

also

presence

products

of

N%(PF,]

such depending

alkylation observed

gave

the

give

ligand a

on

and/or the

exact

u-aainocarbyne

[Pt(w-dppm)zX,]

give

to

ratios

ddpa.

The 17481.

an

inseparable

This

in

was

insertions

readily

of

or were

[ssl]. by addition

carbonylated

reacted

reacted with

mixture

product

Protonation

used.

Analogous

[Pt(cod)Clt]

cio-[Pt(dapm-P),Clt]. 88

the

(335). were prepared

complex

I)

insertion

IPtz(u-dppm)t(CNR)Xlf.

reactants [SSO].

or

and

(X = Cl, Br. I, [CNO] or {cBP3))

derivative

to give

of

complexes

[Pt,(CO)+Clr]z-.

IPt,(p-dapm)&lp]

(X = Cl

substitution

various

[Pt,(u-dppm),(~-CNR)(CNR)=]'~,

dimers of PhzPCHZNEtZ,

u-carbonyl

PhzAsCH+PPhr, give

to

for CPd(~-dppm)Z(CsP,)Xl

Platinum(I) of

into

CPtz(n-dppm)z(u-CNR)X,1.

[Pt.(p-dppa),(CNR)*]'~ ratios

inserted

by its ipeo carbon only.

with

[Pt(dba)2]

head-to-head

to

dapm, to and

141 head-to-tail

isomers

[882].

2-

(335)

Data

did not distinguish

between this structure

head-to-tall

[PdZ(CNMe)+IrJ spectroscopic

was prepared

data

Initially

diner. X-ray diffraction with

theoretical

sirllar bonds

to

in other

rrsnm-effect

[Pd(CNR),] and

suggested

that

the

[Pt(CNR),]Xz.

complex

(2.697

of the metal-metal

bond

The

dimers.

and

was

structure,

The palladium-palladium

Pd(I)-Pd(1)

long

rather

species

showed a rare unbridged

predlctions.

that

were

from

and the isomeric

2.699 A)

in

a halo (SW),

distance

terminal accord

Although

IR

bridged

in accord

(2.533 A) was

palladium-iodine with

the

high

[883]. CNR

CNR i x--pdI CNR

/ 7” CtiR

(336) 1.8 PALLADIUM(O) 1.8.1 Caaplexes

AND PLATINUM(O) with Group

The complexes Although

CM(PPhS)zLl

the authors

no convincing

with

diffraction.

involving observation

a

liganda

(M = Pd or Pt; L = (337)) have been described. the complexes

for the node

was supported

of (391)

R' = MesSi,

for which X = S, (W).

Nmr spectroscopy silicon

to be tetrahedral,

of binding

(R = Me,C.

of the corplex

pentacoordinate

donor acceptor

donor

RR'N-P(-X)sNR

(338). The structure by X-ray

"assume"

evidence

[Pt(C,H4)LZ]

16

suggested atom,

by the structure

[SSS]. Treatment X = S. or

were

determination. (8851.

Se)

of

gave

was established

that in solution

(=a).

bond between nitrogen and silicon

they present

favoured. which

structures and

this

showed a weak

142

/x

1

‘Pt 1 L' ‘P=NR I

(Sssa) (Reproduced

L*Pi

with permission J\ -p-

from

[SSS])

NHR I

1 SiMeg

JN (3391 The

reaction

between

[Pt(CzH,)(PPhS),]

or CR2Ph) has been CY, R' =We Rearrangement n2-C.S-coordination. readily,

via

intermediates

a

complex

studied. to

mechanism

and

RzP(=S)-C(=S)SR'

The

data

platinua(II) involving

were

hydrides P,S-

and

(R = Ph

consistent occurred

or with

fairly

S.S-coordinated

[886].

Treatment

of

with an excess of CS, gave tPdJPCy,),(n '-C&)1 the switterion [Cy,PCStl. Species of the etoicheiometry

[Pd(PCyb)(CS2)]

and

[PdL(CS,)]

also produced

were

by reactions

(37) and

(38). On the basis

of IR

143 data, and with their insolubility

spectroscopic

these complexes

were polymeric

C(C,P,)Pd(OCOMe)(bipy)l

in rind,

it seeas likley that

[887,888]. Me,CO/CSz -

+ [PdL,(n*-CS2)l

{PdL(CS,))

+ (37)

C(C,F,)Pd(bipy)lCOCOHWej [(C,P,)Pd(propanone)(bipy)][CIOa]

{PdL(CS,)) Reaction

of

tetrahedral

[Pt(PPh,),]

Treatment dppe

or

with

ethene

[Pt(PPhs)(etu)9]

[Pt(PPhs)(etu)(oH2),].

ligands

with

Group

with CSe2 gave

by

15

PhN=S=O was reported palladium(O)

the

and

their

at rates

autocatalytic

[Pt(PPh,)(etu),J

or

[889]. caused

replacement

biphosphines.

chelating

In

data favoured n *-C,se-coordination

of

of the

related [890].

ligands

of [Pd(PPh,),]

ligand. through nitrogen,

stabilities

behavlour

the phosphorus

+

studied.

depended [896].

CPttC,H,)(PPh,),l

-

+

on L'

to

were

They

and

readily

Kinetic

[Pt(PPhS),L2]

by an X-ray diffraction

-

in

indicated

(L = (340) or

was a-bonded

Via

study [897].

(39)

H't(PPhS)sL] 2~4

oxjdised

studies

(39) and (40). That (W)

D’ttPPhs)zLtl

(40)

(341)

(349) temperature

[892.893]. A range of

X = Cl, P. COOH or Me) have been

C894.8953.

[Pt(PPh,)=L]

by reactlons

atom was established

L

have been noted

(L' = PhzPC,HI-4-X:

which

(341)) were prepared

Low

to give

[891].

[Pd(PPhS)Ltt]

[Pt(PPhs)s]

donor

reported

(38)

[Pd(PPhs), (nf-CSe2)]. Addition

to act as a monodentate

Two new preparations

soiution

(etu) was

1.2-bis(diphenylphosphinomethyl)benzene

Complexes

prepared

thlourea octahedral

or

reactions of CSSe IR spectroscopic

complexes

+ [(C,P,)Pd(bipy)LlCC~O,l

The data seemed unconvincfng

of [Pt(PPh,),]

triphenylphosphine

1.8.2

Me2CO/CSz -

+ [PdLz(u2-CS2)]

'*P umr

spectroscopy

on

the

products

of

addition

of

144

PhtMeP

or EtSP

to

four coordinate

(Pd(PPh,),)

or

as the major,

but not exclusive

spectroscopic

timescale

at

[PdLL',] Ph,PMe) A

voltammetry (L = PPh,.

products.

Rapid exchange [ass].

temperature to study

L' = PhZPCbH,-4-Cl.

the

occurred

lssPt

nnr

electrochemical

PhZPCIIH,-4-F,

and

more

reliable

procedure

has been published

for

the

of

on the nmr spectra

for

behaviour

of

PhP(CsH,-4-OMe)Z

The

‘complex

spectroscopy although

an

to

or

be

Both

equilibrium

a

red

+ 4Cl- + (RO),P=O

with

[Pt(cod)2] to give n'-coordinated.

an

indicative

a

cl=--[WL2Clz] (L2 = dppe

mixture

or

formed

The

in

(411

nmr

by

solution.

n'-structure

n2-complexes

phosphaalkene

in

was

M = Pd

was

by

noted

such

reacted

as

with

in which all the ligands were

phosphaalkene

of

L = PPhS;

characterised

n2-forms

n'-coordination,

and Me,CCsP

[Pt(Phz=PC,Ht-2.4,6-Me9)31.

With

+ Hz

shown

exclusively

of

[Pt(PPh,)(triphos)].

~Pt(n'-Me,CCmP)(n'-Ph2C=PC,H,-2,4,6-Me~)z]

CM(PhP=PPh)L,].

was

VI'- and

implied

platinum(O)

an nl- form of (ZB6R) could not be detected

colour,

Ph2C=P(CsH2-2.4,6-Meg)

reaction

between

study

[QOl]. Although

spectroscopy,

(343) on

in

diffraction

of

(41)) (8041.

[Pt(PPh3)2(Ph2C=P-CsH2-0,4,6-Me3)1

X-ray

the solid state

preparation

(reaction

[PtC14]2- + 5P(OR)4 + 2[OH]- ---) [Pt(P(OR)J)b]

19021.

formation

[QOO].

new

phosphite complexes

nnr

the

[Pd(PPhg)(PWePhZ),],

[SQQ].

used

was

indicated

for example

symmetry,

room

[Pt(PR,),] have been recorded Cyclic

(Pd(P(OPh}l),}

complexes with C,

and

formed

or

Pt)

by X-ray diffraction

phosphaalkyne,

[SOS].

with

Treatment

Li2[PhP=PPh]

of gave

[904].

Ph2PNPtbPh2

Y

Numerous were

mixed

prepared

seven-membered

by

complexes reaction

chelate

rings

in which (42)

L and L' were

[905].

in diop

The

complexes.

chelating

dynamic including

biphosphines

behaviour

of

the

[Pd(diop),],

was

145 studied by nar spectroscopy

18101.

Na[BH,J/EtOH

[PtLCl,] + L'

D [PtLL'] + [PtLz] + [PtL;]

Reaction of (844) with which

could

not

[(Pt(344)(CrH,)),]

(42)

[Pt(cod)z] gave a rather insoluble

be

readily

was

formed

With

characterised. (n = 1 or 2). and

orange material

[Pt(&I&)~].

this

could

be reacted

other ligands, L. (L = CO, alkynes or PPh,) to give IPt(244)Ll

Reaction gave

of

(?us),

[Co(triphos)(B,S)][Bp,l

characterised

by

X-ray

(E = P or As) with

diffraction,

however. with

[908].

[Pt(CoH4)(PPhs)2]

in which

the

platinum

has

CM{N(CH,C&PPhz )a 11 M = Ni or Pd) reacted with P4XB (X = S or Se) to give (246). The t CM(np,)l; nickel complex was characterised by X-ray diffraction and the palladium inserted

into

the

S-As

complex was assumed

X.8.3 Cumplexcs

The

neutral carbonyl some o-bonding transferred strength.

Croup

of

metals

donor

absolute

complexes.

The known

for calculation

SAsz

ring

[907].

[908].

ligands

electronegativity

This would

the metal

of

of multielectron

the

used

was

act as Lewis bases, and carbon monoxide

to

the

carbonyl of

ionisation

that electron in proportion

[Pt(CO),]

of the transition potentials

state

and

to

show

was dominant with density would be to

[Pd(CO),]

the mean

transition

as

an

oxidising

agent

towards

K,[Pd(CN),],

method

energies

complex systems was studied.. [Pd(CO),] was considered

acted

bond

were predicted

into the semiconductor

and electronic

that

as a Lewis acid in

imply that w-bonding

It was predicted

instabilities

[909]. The Introduction

[NH,][CN]

X4

being induced.

from

of

to adopt a similar structure

vith

concept

transition

edge

[910]. yielding

KzCPd(CN)a 1 C9111. 1.9 PALLADIUM

Accounts

AND PLATINUM

CLUSTERS

have been published

of carbonyl

phosphine

clusters

of palladium

146

and

platinum

[912].

and

of

transfer

reactions

[913].

catalysis

considered

syntheses

and bonding,

chemical

palladium

An

clusters

excellent of home

reactivity,

Trimcrlc

and uses in catalysis

(1.00 As.

0.00

S)

S

in

hydrogen

clusters

clusters.

in

structure

[914].

from [SOT]) (0.56 As, 0.44 S)

(0.44 As, 0.56 S)

clusters

A new topological the effective

platinum

of the sites in the AstS ring are As(l) AS(~)

1.9-l

catalysts

of

and heteronuclear

(346) (Reproduced with permission The occupancies

as

review

atoaic

electron number

counting

theory

based

rule has been developed

on Euler's to predict

theorem

and

the electron

147

counts

of

a

r~Ptl(co),),l*-

also

similarly

be

X-ray

(347)

reacted

obtained

prepared

[M,(CO),L,] An

of

L = PPh(CMe,).

diffraction A

new

study

of

synthesis

clo-[Pt(PMezPh)2C12]

has

were

within

interaction

Relatively characterised. sole product.

to

[Pt,(~-SOa)s(PCy,),J,

[Mp(CSt)zLz]

platinum

were

were, however,

X-ray

too

The

sulphur

y-

-s

which

CPtS(CSz)l(PCy,),]

complex

An

described.

distances range.

give

long

atoms

revealed

the

structure

from

dfffraction

LizS

study

for formal capped

was

formed from

or P(CMe,),).

[PtS(~s-S)=(PMeZPh)Z][BEt412

each

and

showed

bonding.

but

face

the

of

[SlS].

L-M

three

including

clusters

or M = Pd. L = PPh(CMe,)*

the of

been

the platinum-platinum

{Pt3) triangle

SOP

CPtO(CO),(PCY,),l-

[SlS]. The species

(M = Pt,

[917].

with

from

that

and

metal

polyhedral

c9153.

[Pt(C,H*)2(PCy,)] could

number

large

few

palladium

Palladium This was

bridging

formed by reaction

2

\ M-L

‘S-4~~

isonltrile

clusters

have

vapour reacted with CyNC to give rather

CNCy

similar

ligands

to [Pt~(CNCMeS),]

[SlS].

IPd,(CNR),]

(R

previously [P&(CNCy),]

with

three

= 2.6~Me,C,H,)

of the ligand with tPd(dba),l or [Pdz(dba),.CHCl,J

been as the

terminal was

[SZO].

1.9.2

Tetraneric

The from

clusters

clusters

[Pt,(U,-CO)sL,]

[Pt(cod)p].

recorded.

The

complex,

was

tetrahedron

with

phosphine

five

tetrahedral

"P

cluster

(Reproduced

of

a)41CBF43t-

ERzPt*(P(Cge,)

adopted

a

a diffraction

head

and

over

all

1.9.3

tail.

In both

the available

Higher

The

study.

nuclearity

topological

unit

spectra

atoms

with

IHBF,l zr flattened

This cases sites

with

the

from

by

X-ray

a

gave

diffraction.

similar

hydrogen

gave

(SSS),

type

structure

very

demonstrate

gIRp11

structure

were

prepare

[QZl])

with

tirescale

terminal

to

19223.

characterised

hydrides

four

to

a butterfly

on the nmr

were

edge-opened

used

said

prepared

spectra

of the PMezPh

and

was

were

permission

(34S).

were

nmr

distorted

groups

in solution

tetrahedral

was

a

technique

nmr

31P

modification was

CRrPtb(P(CMe,),],]

Reaction

CH1Pt~tPPh(CHne*),}41. by

"'Pt

and

carbonyl

similar

of platinum

(348)

The

and

arrangement

Protonation

A

lssPt

monoclinic (Pta}

edge-bridging

[921].

ligands

[Pt,(CO),(PEtJ).]:

the

determined;

or PMePhz)

PEt,CMe,

their

of the purple

structure

(3481,

(L = PEt,,

and CO, and

CZHd

L.

again

to

of

characterised

with

mobile.

that

a distinct

nigrating

fast

1923).

clusters

electron

counting

theory

developed

in

[915]

was

applied

149 to

a

wide

rPtS(CO) for

range

ssl ‘-.

the

conversion

Quinone

could of

presence

be

a

(Ptz4)

Using was

a

core

water

was

limited

Layered

[925]. An

of

with

an

a

of

water

cubic

for

of ion were

were

parameters determined.

hydrogen

in

[Ptis(CO),,JZstudy

close

llgand, L.

[P~(CO)Ir]z-, rate

or

of

diffraction a

The

[Ptlz(CO)n4]2using

phosphfne

catalysts,

including [924].

Therxolysis

excess

suitable

conversion

by

X-ray

fragment

coapounds

hydrocarbon

oxygen

hydroquinone

cluster

aount

but

clusters

[Pt,,(CO)ZZ]2-

to

to

a

metal

and

[Ptt*(CO),,]'-.

isolated,

[926]. and

of

reduced

platinum

nitrogen gave the

transition

of

[PtSS(CO)oo]r-

exchangers,

that

structure.

EPt~4(Co),&l*obtained was

L,

CPt(CO)L,l

prepared

under

revealed

packed

the

and

having

exhaust the

gas

formula.

in which A and B were metals and D was a CAx'+By3+(OR)+x+sy-n(D)~~-].~R*0. and 0.5hx/y 0.

polyanion.

IPt,m(CO)~6]'-

19271.

(319) (Reproduced with permission

Carbonylatlon The

{Pdm) caps [928].

of

[Pd,,(CO)1Z(PBu3).]

polyhedron

was

a

gave

four-capped

from 19231)

[PdIO(CO),,(PBu,),]. octahedron

with

(351).

unsymmetrical

150

(S51)(

Reproduced Butyl

1.9.4

Hcteronucleur

A

discussed

review

with

permission

substituents

from

[928])

omitted

clusters

of

platinaboranes

rrachno-[(CO)(PPle~)*HIrB=H~~]

interactions

cluster

novel in

considerable with

KH

and

detail

in (9291.

CPt(PHeS)tC1zI

letalloboranes Reaction gave,

of in

a

151 6,6-(PMes),-asyff-9,9.9,9-(CO)-~~do-H-cfre~)*-a~~c~~o-6,9-

yield,

12 4

platinairidadecaborane. the

structure

with

related

MeCN)

with

could

(3521.

Although

be assigned

species

using

Reaction

[930].

cis-[Pt(PWezPh)rClz]

gave

an nrr of

X-ray

diffraction

spectroscopic

the

that

the bonding

the

sane

as

and

stereochemistry

about

the

metal

in comparison (X = Me,S

or

[931].

from [930])

molecular

proposed

arachno-[(Me,P)zPtBsH101rH(PMe9)2(CO)J.

failed,

n~do-[8-C1-7.7-(PMe2Ph)z-7-PtBS0H1,J,

(Reproduced with permission

of

Representation

data

arachno-6.9-XzBloH1z

(353), together with 6 X nido-[7.7-(PMe~Ph)~-7-PtBS0H~zJ

(352)

study

Nmr

spectroscopic

about

Pt(8)

atoms

in

and

of

structure evidence

Ir(9) are

suggested

essentially

1

I(MezPhP)2Pt&Hiz

and

[(OC)(Me3P)~HIrB,ff,,ClJ respectively.

Reaction

of [Pt(C,HI)(PPhs)zJ

R was an aryl group at

least one other

[9321. Treatment gave the

of

bearing

with RIIgCl gave

chlorine

atoms

site on the ring. Many [M1(PPhS)s(CO)]

with

[(PhsP),CIPt-HgRJ

at the 2- and B-positions spectroscopic

[MZ(PhCN)2C1z]

data were

tetranuclear

cycloretallated

species

species (3=)

[(PdW(Cp)(p,-CO)(u-Col,(pPh,)),l reacted

with

Na[M]

and at

provided

(Ml. Mz = Pd or Pt)

(S54). The complex with M1 = MZ = Pd reacted with Na(W(CO)S(Cp)] known

In which

to

to give

[933]. give

The (356)

[Mo(cO),(Cp)J or [Fe(CO),(NO)J). Chromium and tungsten (M = [Co(CO),J. complexes could also be prepared and one aetal could be replaced by another 19341.

152

{3!5S) (Reproduced with permission

Treatment (351);

the

of [M(PPhS)+Xz]

complex

[935]. Oxidative also

gave

for which

addition

u-phosphido readily

[931])

(M = Ni. Pd or Pt) with Li,[W(CO),(PPhz)z] M = Pt

was

characterised

by X-ray

gave

dfffraction

of [(OC)&l(PPhrH)] such as

complexes to

(M = Cr. MO or W) to platinum(O) [(OC),M(u-PPh,)Pt(cod)H], which yielded Similarly, CPt(Ct&)(PPh,),I

(3543). since I(OC),M(o-PPbz)(u-g)Pt(PPbv)z],

rearranged

from

[(OC),M(p-PPh,)Pt(H)(PPh3)21

the

also rearranged

initially

easily

19361.

foraed

adduct.

154 phosphorus in the

atom

of

the

an unprecedented oxidation

phosphaalkyne

new of

cluster

was

type

coordinated

CPezPt(~s-E)z(CO),(PPh~~~l

coordinated

19411.

The

chalcogens

(E = S.

CPe~Pt(~o-EO)(~,-E](CO)=(PPh,),l.

se

use has

or

for example,

to all of

three

organic

been

was Tel (362) (9421.

metal peracids

examined.

atoms for Thus

converted

Y0

(OC),Re-Tt-Re(CO), co

QQ b-

c(15) b

C(12) C(13)m

(-1)

Metal

carbonyl

c(211 O(91 et 1 r,311\

(Reproduced

with

permission

anions were shown to insert

from

[941])

into the palladiun-phosphorus

to

155 bond

of

[PdPt(u-dppm),Cl,]

similarly,

The

bimetallic

[Pt(CzH,)(PPhl),] species

complex,

to give

for example.

regioselectivity

(383). Na[Wn(CO)s]

reacted

[943].

reacted

CMoRh(~-CO),(CO)(PPh~)~(Cp)l.

[HoPt(u-PPh,)(CO),(PPh,),(Cp)]

with

and the trimetallic

[MoRhPt(u-CO)p(~-PPh*)(~-l-o:l-2-n-C=R~)(PPh~)~(Cp)],

oharacterlsed

by

ligands,

Mo-Pt

o-bonded

to give.

again with excellent

the

X-ray

The

diffraction.

bond

by

PPhr

and

to platinum and nf-coordinated

Mo-Rh the

bond

Rh-Pt

to rhodium

(384) (Reproduced rith'permission

ms

bond

(S84),

bridged by

a

by two

benzene

CO

ring.

19441.

from [944])

has been reported this clusters year. (PtOs,) (S4BS). was prepared from [OS,(CO),,(U,-S)] and IPtOs,(CO),(PMe,Ph),(~~-S)l. Further

work

IPt(PMepPh),].

on

and uas

characterlsed

core was a distorted

tetrahedron

to

atoms.

the three

osmium

by diffraction

with the platinum

The sulphur

bridged

techniques.

The

{PtOs,)

atom unsymmetrically

the three

osmium

atoms.

bound and

156 one

carbonyl

several

was

semi-bridging

[945].

other

products

sulphur

bridged

also

last

the

of

of

COs,(CO),,l

thought of

to

formation

with

of

first

to

CPtos,(CO),,~PPh,)(rr,-S),1

and was

characterised platinum via

by

and

X-ray

two

bond

(365)

Reaction tetrabutyl longer rather

of auonium

long

salt

to be

with

(Reproduced

with of

(367)

contact considered

X-ray

face.

diffraction

Photolysis

to

no

in

mixed

inftiate

contrast

of and

by

to

clusters; reaction

major They

a third

with

product were

clusters

from

bonding

each The

1948).

of

were of

the

one

others

(9451)

trana-[Bu,N]p[(C.FS)zPtCltl in which

carbon

[947].

permission

distance.

gave

complexes

to one

is

Reaction

Under

both

linked

sulphur

nitrogen

triangular

osmium

sulphlde

and

X-ray reaction

[946].

under

1

the

the

CPtos,(Co),(PPh,),(~~-S)~l. the

a bridging

AgCgO~]

platinum-silver too

atoms and

gave

platinum

diffraction.

osmium

a metal-metal

including

characterised was

CPt(czR,)(PPha)z

monoxide,

decacarbonyl

triangular

species

which

with

[os,(Co),(~,-S),l

the

that

and

species

(3-I.

these

CPt(PR,),l,

coordinate

showed

[PtOsd(CO),(PMe,Ph),(u~-S)l

CHPtOs,(CO),(PMe,Ph).(PMe~C~H~)t~~-S)l. The

study formed

these

{PtOsz}

gave

[PtOs3(CO)s(PMe,Ph),(~~-S)l

diffraction.

thorough

IPtOs,(CO),(PMe,Ph)z(u,-S)l In the

IPtOs,(CO),,(PMe,Ph)~(~~-S)l. that

more

were

CPtOa,(CO),)(PMe,Ph)~(~~-S)l, indicated

A

silver

gave

had

one

silver-silver A similar

metal

close

the and

bis one

distance

was

skeleton

with

157 a

flattened

butterfly

{Pt(C,H,)((PPhS)z]

structure

and

was

established

[Au(CN-2.6-MeZC.Hs)t]+.

for

The

(368).

prepared

gold-gold

from

distance

was

2.59 A (9491.

CZ3

-c24

from [9461)

(3g4B) (Reproduced with perrission

CNR

RNC

I ,AU\I

Ph3P-Pt , \ RNC

mm New

(366)

strategies

reacted

[Hn(CO)s])

with

to give

preparation

traingulated

tram-fPtMzLz].

were

to

give

bridged of

Reaction

CPttrrz(CO),(PPh,)sl, the hinge and platinuw

[Au(PCy,)Cl]

to

for

characterised:

the

metal

core.

of the type

all

In the

(L = PhCN or

[U(Cp)(CO),]

for which

t(CO)e(PRdrl.

and

the L-Pt(J)-Pt(I)-L

at the wingtips. a catalyst

pfatinuw

give

[Mo(Cp)(CO),l.

complexes

CPt#*(Cp)

clusters [PtC,C&j

L = PR, An

As

reacted

with PR,. Many

possessed

a

58-electron

planar clusters

unit as in (33Q) [MO].

right

be expected

for alkene hydrogenation

species

or

alternative

with ~IrtCO)(PPh,),ClI tPt,,(CO)z*I=which had a butterfly structure with Iridium

the corplex was triangular

the

retal

Whilst

of rnm-[Pt(W(Cp)(CO),)t(PhCN)z]

isolated

parallelograw

the [M(Cp)(C0)9]-

The

of mixed

([Ml - (Cr(Cp)(CO),].

was the reaction

corplexes

structure

the preparation

NafWl

CW(CP)(CO) 91-

with new

for

MO or W) have been developed.

(Ptdft 1 (M - Cr, RNC)

I ,y--pph3 Au CNR

cPt,(rr*-CO)s(PCY,),1

CPt,Au(uz-CO)~(PCY,).J[PP.I.

(370).

gave atom

at

its

open

reacted

with

from [951]. in

which

the

158

fragment

{AU(PCY,))

The dimercurated

occupied

carborane,

an apical

site

above

(371). reacted with

The

topological

heteronuclear

[HPdsPes(CO)t4J"monoxide

19241.

atmosphere

two

solution

The

cluster.

trigonal

electrons.

The platinum structures

and

isolation

little

[PtRh5(CO),S]similar and

a

of

of

and

with

platinum

atom

in

Nat[PtClliJ with

of a strong

[915] was

RhClb

base

under

yielded

was

in

site. however, fluxional

was

(375).

This

metallic in

the

and

72

not the same

behaviour

19541. Controlled

76

were

pyrolysis

applied

carbon with

favouring

valence

by

"C.

loaRh

[PtRhs(CO)I,]-

[PtRh,Z(CO),,]6-.

(374).

species

obtained

(MIa)

centre.

was

clusters analogous

also (37s)

to

and

a hcp

CPtr Rhi a (CO)t, I’-

and and

allowed

latter The

the

interconversion cluster

(373),

coordination

r

in both species,

studied of

a

and

[PtRb(C0)15

equilibrium

of carbon ronoxide

with

clusters

[952].

[PtRh4(CO),z]z-

This is the first example of a facile

[PtRhk(CO),,]*-.

structures

developed

species

triangle

from [950])

CPtRh,(CO),,lf-.

pressure

[PtzRh,,(C0)z,]3-,

(PttRhs(CO)rz]3-,

theory

latter

bipyramidal

lasPt nmr spectroscopy the

Reaction

with an increased

[PtRh4(CO)~+]'-, [PtRh.(CO),,]-

counting including

in the presence

CPtRh,(CO) **I-.

and

of

electron complexes

{Pt,]

[PtLs] to give (372) [953].

(369) (Reproduced with permission

to

the

and

(374)

a

from had

arrangement

reacted

with

159 CRh(CO),(MeCN)Zl+ to give (Pt,Rhfz(CO),,lX-. (376). and on protonation vfa a aultistep process. [PtRh13(CO)2s13-. (377) [9551.

{SYO) (Reproduced with permission from [SSZ]) For reaaons of clarity the cyclohexyl rings have been omitted except for the fpro carbon atoas +

PtL3

(371)

(372)

(Reproduced with permission from E9531)

c

160

(SVS) Each surface bridging

metal

carbonyls

l

(Sy4) (Reproduced with permission

atom bears one terminal (X-bridged

found to be disordered

edges).

The

from [9!55])

CO ligand and is connected second

platinum

on the outer shell. without

atom

any evidence

to two

in (SPS)

was

of a prefered

location.

(ST51 (Reproduced with permission

The

structure

consists

(Pt-Pt, coincident

with

of

three

condensed

the

ideal

threefold

from [SSS])

octahedra axis).

with

a

X represents

common

edge

the bridged

edges

The

fragment

(Pt,(p,-S),(PPh,),}

acted

as

a

bidentate

ligand

towards

161

silver in (378): the intersulphur

distance

was 3.1 A [956].

(t76) (Reproduced with permission

Only the metal array could be established

in a poor diffraction

(377) (Reproduced with permission

The

metallic

central two

skeleton

plstinur

longer

bond8

atom

is intermediate exhibit8

(mean

3.49 A). X represents

2.98 A)

nine and

from [955])

from [955])

between closest short metal-metal two

the bridged edges.

very

study.

long

packing and bee. The bond8 (2-64-2.73 A),

interactions

(3.28

end

162

Reaction

the

I~l ‘-

IFe,PtC(CO) of metal

of

atoms

in which

metals

cluster,

(44) were

the

could

if bonded

studied

[Pt(PPhJ)r]

cluster

[Pe,C(CO),Z

I'-

with

occupied

the

centre

carbide

platinum of

salts

the

gave

octahedron

[9573.

Transition metal

carbide

+

to

by

l13Sn

[Sn9J4-

en _I_)

be

incorporated

the

appropriate

nmr

spectroscopy

into

a

ligand.

hoaonuclear Thus

main

reactions

group

(43)

and

[958].

[L,PtSn,14-

(43)

T

"Sn"

I

en [Pt(PPho),]

1.10

+ [Sn,Tll'-

CATALYSIS

A review been

of

1.10.1

The

dislodge

(II) with

have

of

from

reduction

[963].

A

aldehydes

palladium

COMPLEXES

the

platinum

metals

also

been

accounts

bond

[960]

or

ronocarboxylic

of of

catalytic

of

alkenes,

acids

formed

in catalysis

of

reactions

complexes

has using

of palladium(I1)

as catalysts

[Sell.

over

palladium

hydrocarbons. [962].

which

sulphide

seemed

Palladium

carbon-nitrogen

(379)

were

reduced

to

to

bonds was

and

useful

[964]. the

nitrogen

P-naphthol

was

able

phthalocyanine

double

f ram HI [PtCls]/SnC1,/Me,CHOH

of

of

alkenes

site

reduction

complexes

l-(2-pyridylazo)-2-naphthol.

C6-C.

aromatic

the

catalyst

selective

Unsaturated

(44)

hydrogcnolysis

presence

alkenes

the highly

of

pyridine

hydrogenation

the

the

nitroarenes

PLATINUM

complexes

There

and

of

by the

of

AND

a palladium-palladium

rate

catalysed

presence

use

Hydrogenation

decreased

for

the

[959].

with

or platinum

[LtPtTISns]"-

BY PALLADIUM

published

complexes

-

saturated containing

orange

and

analogues ligands

in

the

including

3-arinocourarin

163

derivatives palladium

[Pd(acac)p]

was

[966].

selectivity

of

Palladium(O) acids

rather

a

and

heterogeneous

reduced

to

hydrogenolysis

terminated

before

acclimatise

Anacystis

with

used

nidulanes

was

that

methyl

a

to q aximise

and

were

mainly

(380)

conversion

alizarin

revealed

yielding

catalyst,

was

of sulphonated

to cold

homogeneous

of methyl-2.4-hexadieneoate

selective

to prevent

generally

complexes

in order

between

Benzothiophene

77 5:

was

reaction

comparison

for reduction

catalysts

2-hexenoate

the

A

[965].

maximum

selectivity

complete

[967].

to hydrogenate

fatty

[988].

H*[Pt Cl6 I, SnCl*

(379)

Palladium the

complexes

reduction

of

conversion,

since

not readily

reduced

and

hydrogen

containing

I-alkenes

gave

a

dark

of azlactones.

defined,

it

semms

were

brown

that

solution

(381),

was catalysed

Crosslinked

polystyrene

used as a catalyst anchored

to

atmospheric little

competing

converted

to

was

its

2.4-diisocyanatotoluene

complex

95 4

which

were

enantioselective

active species was poorly

reduction but

ita

was

of ArNOZ

involved to ArN&

structure

was

.

not

of (3112) to

19721.

thia year have been polymer bound complexes.

a

useful

[974]. with

with

reduction

Rates were dependent

isomerisation

for

at

1-phenylethylamine

of the 2-, 3- and 4-isomers

was functionaliaed

polystyrylbipy

alkenes

interaediate

by PdCl,/trioctylamine

described

catalysts

98-99 %

catalysed

isolated,

for the selective

pressure.

which

catalyrred

was

dihydroxylamines

was

Internal

cycloaetallated

[971]. Hydrogenation

catalysts

to

the catalytically

a

fully elucidated

Numerous

were active

of PdCl= with chiral

truos-[Pd(py)ZXz]

probably

anines

selectivity

isoaerised

Although

likely

f970]. The complexes interaediate.

primary

alkenes;

[QSQ]. Treatment

reduction

An

to

alkynes

[Pd(bipy)Clt] of 1,5-cod

catalyst

for

alkene

on steric hindrance

4.4'-Diamino-2.2'-bipy Pd(OCOMe),,

to give a polyurea.

and the product

[973]. Pd(OCOMe),

and

On reduction

reduction

at

and there was was

prepared,

polymerised

with

with Li[AIH,]

a good

164 catalyst

for

alkene

functionalised

hydrogenation

was

(383). was

polystyrene,

the catalyst was very active,

obtained used

C975].

The

in reduction

and had a long lifetime

anthranilic

of ArNC&

acid

to ArN&

and excellent

;

stability

[9763.

PY

PY . _

1/Cl,

EtoH\

17

'w

RN

\ - o/W~cl~ I I

b I

PY

-A

4

9-_llrR

&

i H--b

PY

-0'

co2

Et

-0'

co2 4

(982)

(981)

A

soluble

homogeneous

polyvinylpyrrolidone, supported supported reduction produced catalyst system

on

PdClp

silica

and

polyrethacrylic of RNOz.

N%p[PdC1,].

alkene

uaed

gtSN for

catalyst

[977].

nitroarene

of X,4-cyclohexadiene

reduction

On reduction,

was

palladium

188

prepared clusters

obtained

material

has

hydrogenation

and platinum

aldehydes

alkenes.

This

from

also

19781.

complexes

were

[979]. The

and ketones

of polyethyleneirine/PdCl~

for reduction for

and

acid palladium

ArNO,.

on treatment

reduction

been Silica

used in species

with Na[BH,] was a selective

to cyclohexene by

[SSO]

impregnating

of diameter

A catalyst (384)

35~10 A were

with formed

[981].

It

has

been

known

for

some

time

that

palladium

complexes

of

silica

165 modified imines has

by

y-arinopropyl

and

now

been

modifying arines

nitro

studied.

The

with

and

19831.

conditions

A

rate

salts ketones

by XPES

could

also

complex

of palladium zeolites. the

chloride

with tertiary

macroporous

and

of

grafted

catalysts

hydrogenation

[985]. PdC12/RBN

supported

catalysts

for the reduction

palladium

complexes

catalytic

of alkynes

have been related

Hydrogenolysis of

structure than

reduced

of

PhCHzCH=CH+ of

the

tertiary

under

ambient

silica

supported

catalyst

and has been

[984].

nacroporous

variety

of

the

be

alkynes,

alkenes.

reactions

was a reduction

preactivation

a

of

on

slower

platinum

The grafting and

depended

giving

poly(3-diphenylphosphinopropyl)siloxane studied

reduction

hydrogenation/isorerisation

reaction

ammonium

Aldehydes

catalysed

The

compounds.

amine.

[SSZ].

groups

sources.

hydrogenolysis

and

For

enhanced

on inorganic

studied.

was rate

of

oxides

hydrocarbon

provided

useful

activity

Na[BH,CN] of

(886)

was

[988].

of

[987].

has this year been accomplished example,

The

[SSS]. XPES studies

to their catalytic

decarboxylation

halides were reduced to 1-alkenes

the

to cis-alkenes

of ally1 derivatives

hydrogen

anines on to microporous

adsorbants

used

using in

whilst

the

ally1

using Pd(O)/P6u,/[i-ICOD]- (9891.

(385) Hydrogenolysis

of

( CMhl

= EPdtacaclp I.

modest,

selectivity

synthesis

of

anion,

high

and

of

PdC1,/Et,SiH/BtSN

benzyl

or

accomplished

[Ni(acac)t]/L). was

ally1

ethanoates

electrophiles,

esters

thus

spodopters

of

of

to react with

was

(386)

pheromone

hydrogenolysis

able

Hydrogenolysis

Catalytic

sulphones

[Pd(acac)p]/PBuS was

the

Electrochemical ally1

alkenyl

was

was

achieved

using Whilst

prepared

for

BuMgX/[ML,] yields use

also

been

noted;

the first product in

the

[990,991].

littoralis

has

were

in

the

an

19921.

presence

of

[993].

oxidation

and

H/D

exchange

of

alkanes

in

the

presence

of

platinum

group

methane

by

repulsion and

stretching of

groups

using

PRS

was

then

ion

D20

[998]. of

to

substrate,

1.10.2

but

of

electron

Carbon

[lOOl].

TrO

4-position it

and

The

of

as

when HCl

propanal

palladium

a perfluoroalkyl or HL[S04]

the

presence

obtained

alkenes

of

and

however,

using

in

catalyst

was

[lOOS]. were

mild

the

Without

the

with

PdC12/CuC12/C0/Oz/HC1

the

=

3

or

related

4; to

mechanism

of

%[PtCl,] as

reaction,

whilst

70 %

was

yield

at

using

in

active

of

the 1 atr

of give

added

increased in place

2-•ethyldecanaote

Branched

esters

were

of in

also

PdCl~/CuC1~/CO/O,/HCl/ROH

and

as

the

of

the

reaction

cyclic

catalyst,

was

achieved

4-(2-Methypropyl)-l-ethenylbenzne

peracld as

to

carbomethoxylation

products,

been

presence

alkenes

was

[Pd(PR~)2C12]/SnC1,

used

the

dichloride

methyl

the for

or

has

[1002].

[1005]. with

[Ni(CO),]

catalysts

the

major

to

only

a

67 %

added

and

was 25

mainly

yield

alcohol

product

pressure

give

was

1n the

a

linear

obtained

reaction

of

RCH(Me)CO,CHzCHzOH,

lC,

using

was

reported

I-decene

as

[lOOSI.

Enatioselective in

the

Nafion

mainly

c10073.

RCH=CHI

Optimfsation

was

ArCH,CH(NH,)COOH

occurred

or powdered

major

conditions

yield.

about

presence

and/or

of 9.3:1

yielded

Using

ethane-1.2-diol

78 %

the

[Pd(PPhs)zC1,]/CO/H,0/HCl/3-ClCsH~COSH

90 %

in

in

carbonethoxylation

also

When

substrate

reaction

platinum(I1)

1-alkenes

[1008].

obtained

simply

A

alkynes

propene

ratio

acid

Decene

from

esters

rather

under reacted

in the

sulphonic

alkenes

linear

not

accelerated

and

PdCl,/CuCl,/HCl/CO/WeOH

this

internal

was

C-H

methylene

(n

[Pd(PR,),]

all.

agents

of

catalysed

[lOOS,lOOS].

selectively

system, and

acid

of

as

in acidic

Using

by

[lOOO].

carbonylating

Hydroforaylatlon

a-methyl

rates

platinum

finally

at

[999].

trans-1.2-bis(diphenylphosphino)cyclobutane butanal

rate

reactants

the

[996],

of

rcac&ions

complexes

reviewed

or

and

exchange of

the

of

discussed

H/D

exchange

ring

retarded

cyclocarbonylation

palladium

aryl

in the

groups

also

activation

As

methane,

presence

DpO

The

distortion

the

reaction

not

with

the

donors

monoxide

the

did

by

[997]. the

[994].

theoretically.

in

were

in

phenylglycine

withdrawing

The

studies

reported

deuteration

electron

deformatlon

> PPhs),

proposed

studied

was

pentane-2.4-dione

Reaction

reviewed

decreased

concentration

was

> PMePh,

since

been

was

H-C-H

Kinetic

chloride

= PBu,

led

has

energy

by

[995].

effect

pKa.

complexes

rrano-[Pt(HZO)rCIZ]

approached, complex,

metal

hydroformylation

enantiomer was

achieved

excess by

of

using systematic

ethenyl

benzene

[Pt((-)-DBPDIOP)C~,] variation

of

the

as reaction

to occur catalyst. parareters

167 [lOlO]. Platinum

chloride

best

reported

so

far

Hydrocarboxylation yields

using

of

supported for

(388)

fPd(diop)Clz]

on (387) gave similar optical

a

and

polymer

(389)

gave

supported good

catalyst

chemical

but

[pd (diop) CO,

Oxidative

the

with

good and

(395)

in

was

major

2-alkynes

selectivity

EtOH

product

similar proposed

of and

gave

I-alkynes usually

being

a mono

e8ter.

(392)

Reaction

of the

only

[1013].

PdCl~/CO/HCl/H~O/[Bu.N]Cl carboxylic

optical

Ct21

hydrocarboxylation

being

process

[loll].

poor

0

-J-------V

However.

the

[1012].

0

former

yields.

quantities [10143.

(390) obtained

was

Hydrocarboxylation

gave a complex

acid8 and some butenes.

mixture

R

PdCl~/Cucl,/Hcl/o,/R'OH/co l

R'f. 1 atr. 2 hr

)-7 R’bOC i-0)

COOR’

again

(393). gave

a of

mechanism

with (394)

for

butadiene

of aaturated

the major product

[lOlS].

R-CmCH

obtained,

a.o-diyne.

(2:1-1.26:1);

and (391). the in good yield.

the

using

and unsaturated

being I-3-pentenoic

acid

168

R

PdC1~/CuC12/"c1/CO/R'o"/OZ -_---___---___--___-______-+ RT. 1 atm

R-&C”

R R

G -

d-HN

wx2

co+

+

dOH tu

= R

AR (a=)

Reaction

of

Cf’d(PPha)rCltle

mechanism

carbon

ethene,

PPh3 and tfaH gave

of reactions

[PdL4] + "X w

I”Pdb,N [EtPdL,&]

of

95-99 % selectivity.

The

[lOlS].

(45)

(46)

+ C2", V

[EtPdLld(]

(48)

+ CO v

[EtCOPdL,,&]

(49)

+ CtHI -+

[EtCOC"&HZPdL,,,X]

+ "X + PPhs b

of

of

yield

halides

reported

palladium

could

catalysts.

acid

was

Par

used

reacted

as

In the presence

the

aryl

halides

exarple,

converted

pyrldine be

of

to

using

benzaldehydes

similarly

hydrogen

[1018].

donor

of an alcohol

[1020]

and or

esters were produced.

reacted

2-¤ethylpropenoate

also

[1019].

(51)

carbonylation

broaobenzene

as the catalyst

[1021] benzoic

Alkenyl

+ [PdLpX,]

2-Promo-6-phenoxy

[1017].

Poly(nethylhydroailoxane) [Pd(PPh,),J

(50)

EtCOEt

have

patents

presence

the

methyl

presence

[PdLa] + CO2 + 2"X

CO/",/[Pd(PPhS)&l,]/PPhJBu~N,

phenol

with

the

147)

P

number

in 88 %

3-pentanone

in

["PdL,&]

[EtCOC"&HpPdL&]

in

hydrogen

["PdL,,,X]+ HX

Hz

[EtCOPdL,&]

A

and

(45)-(51) was proposed

[PdLZXt] + 2L + HZ0 + CO I

CPdLzXzl +

monoxide

siailarly. in

the

Thus

presence

2-bromopropene of

was

converted

[Pd(PPh,),C1,]/CO/(MeO)ZCO

to at

169 150

'C

and

flO221,

CHZ=C(CF~)COOH of

110231.

may

RCH=CBr=

be readily Allylic

proposed.

halides

MeC(R)=CHCH,CHO ArCHoCOOH

was

Carbonylative to

occur

In

situ

[1029]

In both

cases

(t)-A5(iz)-capnellene

R,Zn.

was

reacted

;x

of

thought

sirllarly

+

the

transfer

conditions

Although

reaction

none

definitfvely

was

the

presence

demonstrated

were

as MeC(R)=CHC&X

in

(for

presence to

give

mechanisms

[1024].

carbonylated

to

Carboxylation

[1025]. of

[W{RzP(CH2),PRz)X2]

an

halides

alkenyl

true tin

catalyst

was

compounds

(52) and

the

aldehydes

of Arc&X (M = Ni

(55)). A

aryl be

and

formed

(reaction

R3s-;;

related an

in

(57))

or

to

or

(ROTf)

halide. [1031].

a

The

(56).

also

tin

formed (54))

also

dialkylzinc

Alanes.

aryl

useful

synthesis

reaction

formed

of

involved compound, in

sftu.

110321.

I Pd(PPh3)2C121

R3h

(52)

d’

CPhCHZW (PPh&Cl

R4

FfR

I

4-J-A

(531

0

&a/Cl

+

Pd,

shown

(reaction

were

in

was

complex,

sirilarly

process,

alkyl sftu

(53))

alkenyl

used

was

(396)

and

a palladium(O)

reacted

trlfluororethylsulphonates

[lOSO].

to

reactions

example.

or

the

Ally1

(reaction

cross-coupling

in

phase

allylic

alkenyl

substrates

CO

to

[1026].

[1027,1028]. and

with

transformed

E-RCH=CHCOOH.

coupling

between

compounds.

reacted

Hz/CO/CPd(PPhS)zBrz]

achieved

n < 3. X = halogen)

under

analogously

yielded

such

using

be

E-PhCH=CHBr

However,

[Pd(dppe)2]/benzene/NaOH/H,0

Ar-CnC-C-C-Ar.

could

CH2=C(CFb)X

/LfSnM=3

hd WeCN)2Cf2 J )

A /

\

PPh3 I CO up

to 75%

(54)

170

I w (Pph3)41 Co

SiMe

LiCl

3

(%’

86 ‘la

IPd(PPhe),]/CO/Zn/Cu ArX + RX

) ArCOR + ArR + ArH + ArAr

(56)

1 atn, thf 80-90 x

CPd(PPh,),l RBr + CO + Al(OR*),

) RCWR'

A range of double carbonylations Thus

iodobenzene

PhCOCONEtr

of

gave approximately

PdC1,/Cy2P(CHz)zPCyr

PhCOCONEtz gave

to 98 %

useful

including

"C

derivative. using

CyNH+

equal yields catalyst anines

An

labell_ing study,

as well

the expected

PhC(=NCMe,)CONRCMe, 110381. A mixture

[1037]. The of ArzCO

of palladium

salts.

co

[email protected]< COR

the

[1033]. The

LaMCOCOR proceeded

(93 %),

towards

halides

reaction

iaine became

was not an via (397) and

in the presence 7 X of

the

the major

and ArCOCOAr

the pressure

also

nechanisr.

of

irine

product

(4-20 %) was

[Ar,I]X. with carbon monoxide

of ArCOCOAr

give

of CO resulted

in the in the

[1039].

,CONu

Nu

La



B

RCOCONu

'COR

(397)

(399)

Reaction of nitrobenzene studied,

to

selectivity

that

(38-88 X)

Increasing

formation of an increased proportion

this year.

PdClz

or benzilic

of

PhCOCONHCMe,

by treating the iodonium salt,

and

new

slectivity

with CO to give the isocyanate. PhNCO, has again

catalysts

[Pd(py)zCl,]/[pyH]s[FezC15] high

increased

of iodobenzene with CO and Me,CNH,

as

of

the use of [PhPd(PPh,),i]

and alkyl

established

obtained

Very

presence

of the two products

investigation

presence

been

the

in the reaction, which almost certainly

(998) [1036]. Reaction gave,

in

(9.6 %). although

as

[1035].

(57)

of halides has been reported

CO/EtlNH

[1034]. Other

results

a

intermediate

PdClz

with

(60.5 %) and PhCONEtl

as catalyst use

reacted

+ AlBr,

[1041]. for

systems and

formation

including

[Pd(py)zC1z]

VzOS/PdC1,/Alz09 of

the

Cl0433

[10403,

described.

bis(isocyanate)

from

171 was

2,4-dinitrotoluene

mechanism they

by

low

pressures

and

and a short contact time 110431. In the presence

concentrations, the urethane

favoured

was usualfy obtained using PdCl+/py/VzOs

catalysts of alcohols.

as catalyst

110443. The

of the reaction was studied by two groups but the catalyst

used

were

(reactions

different

and

the

they

mechanisms

proposed

quite

systems distinct

(58) and (59)) [1045.1046]. CO/EtOH ArNHCOOEt ArN=NAr _I_,

PdCll/NaX/FeX, > ArN(-O)=NAr

ArN02 + CO

w

(58)

EtOH co F ArNH, -_, ArNCO -+ ArNHCOOEt

CO/[Pt(PPhS)&lz]/SnCIJEtOH ArNO,

+\/

ArN: Again rather

using

than

(59)

an

selectivities

as catalyst

[Pt(PPhs)zCinl/SnC1~ alcohol

as

up to 91 %

could be altered

the

nucleophile,

(reaction

(60)

to give the arylamine

but with a carboxylic was

ArNHCOR

[1047].

The course

as the principal

obtained

conditions

with

of the reaction

product by the use of

CO/H20 as reagent. Any carbamic acid formed would readily decarboxylate the reaction

acid

under

[1048]. ArNCO

ArNOz

IPt(PPhs)zClz] , ArN : / + 2c0, -2c0, '.\ '\\ ?H,

\r;,""'

+HtO RCOOH, -H,O

'\\ \

\

-cop \

!

/

’ ArNH,

Carbonylation literature. ratio

in

of methanol

the

presence

PtC12/Co(OCOMe)z/LiI [lO50]. A similar of

as

of the

reaction

Kz[PdC1,J/CuBr/KIOCOMe]

converted

in

[Coz(CO),]/PdClz/Bu,P catalyst

system

was observed or

attention [1049].

the major

for higher

in the patent

using CO and I& in a 1:l

alcohols

Pd(OCOMe),/CuCl/K[OCOMe]

However,

product

was

with

MeOCOMe

in the presence

[1051].

(999)

was

to (400) ClO521.

Oxidative occur

has again received some

Ethanol was formed with 73 % selectivity

the

carbonylation presence

of

of methanol

to yield MeOOCCOOMe

was

[(Pd(CO)Cl),]/LiCl/quinone/MeOH/CO/Oz.

reported

to

Bimetallic

172

(PdCOOMe)-containing the

reaction

species

intermediates

interpreted

in

were

terms

proposed

of

both

110533 and

palladium(I)

the kinetics

and

of

palladium(I1)

[1054].

COO (s-1

(1001

Oxidative benxoic

carbonylation

acid

achieved

in

using

the

of

presence

Pd(OCOMe),

benzene

of

OP.

Pd(OCOMe),

under

The yield was increased by addition of CO with

ROH

and oxalates

in the presence of methyl

(1:1.5)

mainly ethanoic formed

the

Using

metal

was

propanone

Fischer

monoxide

Cz-Cs

[lO621.

whilst

the

water

gas

said

to

give

place

of

.

Pd[Ns],

carbonates

gave

shift

The reaction

in

to yield MeCHO [1056],

dimethyl methanol

but

[1059]. Ethanal was

the

alcohols

between

over

By contrast

the

of methanol

Cu.

carbon/Me1

presence

oxalate

and

purported

to

hydrogen

and

Co

or

bimetallic gave

ethanal

were

[1064]. Among

of

dimethyl give

the

Al

carbon

oxide/PdO/alkali

homogeneous

systen,

as

product

the major

systems

for

trans-[Pt(SnC13)ZC1t]2-,

chlorine

to give phosgene was catalysed

complex being more effective

and copper(I)

(61)-(66) [1067]. Oxidation

catalyst

[1065].

of CO with molecular the palladium

copper

uaeful

[PtC1,]z-/SnC1,/SnC1t.

[lOSSI. A study of the kinetics

palladium(II),

in patents

(sic) [lOSl].

reaction

and [Pt(CZH4C1)-

by [M(CO)Cl,]-. analogue

be

[TPPFe]/polyvinylpyrrolidine/platinun/l.2-dimethylimidazole

the formation

PtClz/4PbClz

could

with

PdC1,/RhCIS/KIOCOMe]/active

[Ru~(CO)1~l/K~CPtC1,1/CC7H~~PPhS1Br/SnC1~ [1063],

yielded

[lOSS]. Reactfon

PdCIZ/RhC1,/WeI/KIOCOMe]

Me,COOCMes

in

Tropsch

yielded oxide

promoted

conditions,

as cocatlyst

was reported of

system of

compound MeSCOrCCCOLCMeS

The

peroxide

Carboxylation

using PdCl,/VCl,/MeI/[MePBu,lC1

catalyst

tPd(acac),l/MeOH/py/CuCl

unlikely

severe

a

of Pd)(h/CuClt/N*I& PM*V,a,

ethanoate

Carbonylation

carbonate.

and

(10551.

of Fe[N0319

in the presence

anhydride

using

[10601.

more

CO

110571.

Carbonylation and MeCOOH

using

of CO oxidatian suggested

than the platinum in the presence

the mechanism

of carbon monoxide was also catalysed

of

of reactiona by PdC12 or

173

Pd[SO+]

with NasHzPMoeV,Olo

+

CuCl

CO

(cu(co)Cf)

+

+ CuClz

(Pd(I)(CO)}

__,

(61)

[Pd(CO)Cl,]-

+ CO + 2&O

+ Hz0 ----+ (Pd(O)}

+ 2CuC1,

Oxidative The

[X069].

carbonylation

yield

A

was

similar

lower

reaction

MeOzCCH2COCHpCOOMe

I-10.3

of

(63)

(64)

+ CO, + HCl + H+

(65)

(66)

as in

in

catalyst

the

on

the

presence

gave

absence

of Me(CHz)&ONO

CHz(COO(CH2)~Me)p

of

the

diketene

using

mechanism

[lO70].

quaternary

in

and

86.5 %

ammonium

MeONO/CO/MeOH/PdClr

salt

yielded

Oxidation

in solutions

[1072].

oxidation

containing

Palladium

A method

[10733.

for a

been

Pd[SO,]/HPA

recycling

[1074],

and

110781, [1080].

When

type

oxygen

was noted

I-alkenes

Catalyst

systems

has

oxidation

been

catalyst

surfactant to

quaternary

ethanoic

of l-butene, rather

than

employed

[1079].

salts

was

adsorbed and

on

described have

ketones have

included [1075,10763.

oxygen

carbon

butanone

as

an

The

effect

studied

butane-2,3-dione

as the expected

molecular

containing

PdC1,/CuC1,/CuC1/MeC00H/2n(0C0Me)2/Ht0

ammonium

acid

as well

reviewed

was

methyl

PdC1z/HPA/HzO/decane/CTAB/perfluorodecalin E10773.

to occur

[lO?l].

ketones

and

(HPA)

Pd[SO,]/VO[SO,]/H,SO,

compound

reported

of

ethanal.

catalyst,

to

PdC1,/CuC1,/H~0/N-nethy1pyrro1idone

course

oxidation

alkenes

of

PdCl,/CuCl,/[RNMe,]CI/HLo/PhH reaction

of

a Wacker

oxidations

reported.

by molecular

salts and heteropolyacids

oxidation

heteropolyacid

Numerous

again

of methane

platinum

catalysed

pailadium(II).

in

was

used

were

the

detail as

obtained

[1081].

oxidising

on

some

the from

The use of a

agent

has

been

[1082].

Whilst Wacker

+ CuCl + Cop + 2H+ + 4Cl-

+ CuCl

methanal

by an unknown

The catalytic

nftro

(62)

----_) PdClr + 2CuCl

fPd(FPhs)rBrtl/SnC1,/IBu,N]C1 yield.

+ Cl- + CuCl

+ (Pd(I)(CO))

+ CuC12 ----,(Pd(II)(CO)Cl)

(Pd(II)(CO)Cl}

(Pd(0))

[1068].

{cu(co)c1}

+ [PdCl~I'-

[Pd(CO)Cl,]-

in alcohol

internal

conditions,

alkenes a number

are

less

readily

of examples

oxidised

of this

reaction

than have

1-alkenes been

under

reported.

174 Cyclopentene presence

was

oxidised

unsaturated

with

cyclopentanone

83 %

selectivity

[1083], and Pd[SO,]/HPA/N-methylmethanamide

of PdCl,/CuCl,

to be a useful catalyst the

to

system

ester,

for cyclohexene

(401)

proceeded

oxidation

with

in was

the said

[1084]. Oxidation

excellent

of

regioselectivity

c1oa51. Na2tPdC141,

MeCOOH ’

py--“’

ogJrcooH.

Me$COOH SIMe2CMe3

SiMe2CMe3

(401) Epoxidation

of

1-octene

(402):

alkenes gave

stoicheionetric

oxidation

presence

undefined alkenes were

of

the major

the

reaction

Although

products.

catalyaed

by

[1086].

A

accomplished

catalytic

was

under

an

using oxygen

has

been

to

the

(402)

with

a u-ally1

of Pd(OCOMe)Z/Sn(OCOMe)z/KIOCOMe] have been

reacted

with

be proposed

in

remained bicyclfc

allylic

mathematically, of

92 X

complex,

alcohols

to account

in the presence and

the

selectivity;

the

in the reaction mixture to PhC&OCOMe

clusters. ways

reaction

The

data

and

[lOSl].

in the presence

was said to show three distinct in several

optimal

PdC12/CuC12/HOCHrCHtOH.

and 1.4-dichloro-2-butene

of toluene

palladium(O)

interpreted

monoethanaote

presence

were also detected

of

could

occurred

the mechanism

as substrates,

scheme

modelled

In

study of the oxidation

formation

but

ethanoate

[lOSS].

[1090].

involves

3.4-dichloro-1-butene

involve

cycloalkenes

A mechanistic

converted

probably

A kinetic

to 2-cyclohexenyl

of ethene to ethane-1.2-diol

predicted

butadiene

however.

was

became

was

selectivity

cre-[Pd(NO,)(MeCN),Cl]

with

selectivity

PdCIZ/Pe[NO,]z/WeCOOH

conditions

to

norbornene

of cyclohexene

epoxides,

The conversion

mechanism

of

peroxide

99 %

Pd(OCOMe)z/WnO,/MeCOOH/quinone,

[lOSSI.

to give

for the observed

of

hydrogen with

f10873.

Allylic the

dilute epoxide

epoxidation

crs-[Pd(N02)(MeCN),Cl]: atmosphere

by

the

stages.

presented

[1092]. Oxidation

and

could.

of fluorene

175

in the

presence

9-hydroxy

of palladium

fluorene

phenol yielded

29 %

the quinone:

[1094].

presence

of

Hydrogen

[1093].

but in the presence

phthalocyanine

[PdLzClz].

peroxide

of

chloride

were

by

molecular

[PdCuLzCIZ]

or

[PdNiL,Cl,]

fluorenons

of

and

2,3.6-trimethyl

iron or ruthenium

conversion

(404)

The nature of the catalytic

gave

oxidation

the best catalysts

of palladiua

Oxidation

complexes

salts,

was 23 4; and the yield

oxygen

gave

(405)

in

the

(L = aethfonylmethionine).

species in solution was not clear

[lOSSI.

(403)

(405) 1.10.4 Other additions

Numerous complexes

with

examples

have

with

been

slktncs

reported

conversions

in

to

and the

reacted. unusual of

product,

this

of

the latter

being Other

Thus.

showed

similar

[loss].

(rOr)

both

to

catalysts

the

give

monomer including

The

under all conditions.

to

reacted

give

83 %

selectivity

in

3-Phenylpropene

was

yield and with little isorerisation

a silyl

useful

and platinum

MeHSiCl,

H,[PtCle]/MezCHOH

sllanes were also obtained

and from MeSSiNBCH&H=CH2

giving

CP,CH+CH2SiMeClz.

trichlorosilane.

of

silanes

result

alkene

enol

3.3,3-trifluoropropene a

by palladium

[lOSS.l097].

[llOO]. Linear

[llol],

reaction

catalysed

silanes

[Pd(PhCN)&lz]/2PPha

fluorosilicones. only

(406)

reaction

presence

gave

presence

linear

of Hp[PtCle]/PRS

most

year

to PhlCHZIPSiR s in good

the presence In

alkynrs

trialkyl

phenylethene IllO2].

this

the

and

[lose].

hydrosilylated

ketone

and

of hydrosllylations

1-octadecene

CI,,H9,SiMeC12 their

to

reacted

the

trffluoromethyl

[llOS]. However, with

HSiMeClf

CF,CH(CHS)SiMeCl, for

the

H,[PtFu], is

as

preparation and

doubly

from

and HMeSi(OSiMe~),

and

ether

in

radical unusual

gave only CF,CHzCHzSiC1,

in

the of

in a the sole new

initiators in

[1104].

that

176

(roe)

e

sic13

0

H21PfCt6] +

HSiC13

A

Si Cl3

\

%

‘F3

cF3 (107)

Hydrosilylation boron

Hydrosilylation with 7)

of

containing

of

varying

monosubstituted

palladium

and

1-alkynes

alkyne

platinum

generally

stereoselectivity

and

derviatives

complexes gives

further

has

in been

a mixture

of

the

presence

reported cc- and

examples

have

been

readily

than

alkenes

of

[1105]. g-adducts

noted

(Scheme

[1099,1101,1l06-11091. That

alkynes

demonstrated

by

substituted used

in

the

(411)

the

reaction

in the

ratio

Hydrogernylation

to

now

was

give

and

Numerous

polymers

gave. on

with

R

(414)

reactions

[lllS-11261.

have in

and

alkynes

and

alkyl

patents

The

moderate

presence

of

of

1-silyl

gave

(m).

reaction

yields

of

H2[PtCls]

hydrosilylation

with

WeeSnz

The

related

addition

kinetic

after

hydrosilylation

the

Z-RC(SnMe,)=CHSnMe3.

as

(417)

Hp[PtCls]

[llll].

giving

reacted

complex

depending

of

again

of

of (410)

followed

gaiving

an

mainly

[1113].

RCmCH

of

and

in

C,,Hz,CmCIi

reversible

Hydrosilylation

presence

ketones

that

to

Stannylmetallation

proprtions

[lllo].

the

was

[1112].

studied:

catalyst

in

a-silyl

111141.

alkynes

(4(MJ)

1-alkynes

that

more

regioselective

course

from

been

formation

of

known

[Pd(PPh,)a] have

5:l

similar

was

of

reasonably

E-ClOHzlCH=CHGeRs

of

R-CmC-SiMe,,

synthesis was

essentially

It

hydrosilylated

alkynes.

Me,Si-C-C-COR and

are

(41s) using

work-up, the

reported

(412)

were

the

the

(416)

substrates the

use

preparation

and

of

presence

reactions gave

of

(413),

and

(416)

and

predominated

of

allenes but

thernodynamic

Bu,Sn-Zn(SnBu3)z

a mixture

catalyst.

substituted

the

to

in

its

products

a palladium (417). using

the aryl

[1115]. of

platinum

cross-linking

catalysed of

siloxane

177

C6n,,C~cH

Hz WClsl -

+ RISiH

R3Si/+/c6H13

H,WCl,I Ph-CICH

+ Et~SiH

E-PhCH=CHSiEtS

-

+

+ Et,SiH

Hz CPt’& 1 _1_11, LiI or LiCl

21 %

Et,si-c*C-Ph

or RsSiI

HZcPtCle 1 HOC(Me)r-CmCH

+ PhMeSiHz

MeOCOCH,-CmCH

+ RR'SiH2

Ph-=

Scheme

+

7 Hydrosilylation

-

+ EtSsiCH=CIPh

Me I Ph-Si-0 I

Hz CPtCls 1 ----- ---+ RRtSiHCH=CHCH,OCOMe

+ Et$iC(Ph)=CHz

+

e

1-alkynes

in the

presence

+

+ RR* (CH=CHCH~OCOMe),

Si HM e2

of

t

PhC(SiEt.)=CH,

79 %

Ph-CmCH

R3Si \=Jc6””

+

of Hz[PtC16]

178 SiHMeBu

H$PtC161

J=-+

+ EuMeSiH2

J= ‘r<

__I_$

R

(408) SiMe3

R

Me3Si

)=/

<

Il-1

(111)

(4101

R”

R* +

\wo+R’

R#v

[Pd Wh3141

H

FM=3

R

Me6 Sn2 ?

)=q R’

Et 3%

SiEt3

Sic13

R

OR

OR

SnMg

(412)

R

d-

SnMe3

+

-

6

SnMe3

(4131 (414)

R

d

SnMe3

Y--

SWe3 d’

(415)

1) Bu&n-Zn(SnBu3)J"Pd" +

R-CmCH

g-RCH=CH8nBus

+ RC(SnBu,)=CH2

2) HsO+ (4171

(416)

Addition

of

The

to

ethyne

1-chlorobutadiene

chloroethene. [11273.

HCl

complex

CH,=C(Me)OCH,Ph

the

was achieved by hydrogenolyals Cyclopropanation by diazomethane

and

[Pd(cod)Clt]

to give

the

in

presence of

products

catalysed

protected

of

gave

oligoaerisation

an

alcohol

MetC(OR)OCH2Ph.

across

Deprotection

[1128J.

of strained alkenes such as norbornene

occurred

PdCl,/FeCIS

oxidative

addftion

species

of

in the presence

and norbornadiene

of a range of palladium

complexes.

179 Under

related

NICHCOOEt than

double

bond

with R'R'C=CR%

[RhZ(OCOMe),]

Some palladium alkene

explanation

was investigated.

catalysed

additions

foraed

involving

a

attack

Thus (418)

six-membered

at

the of

proved less useful and low frans:cX8

\

I

(418)

of a nucleophile gave

mainly

chair-like

similarly

PdcI:,/cucl2 ./co

I

low yields

involve

in situ.

[1131]. The reaction of (420) proceeded

I

[Pd(PhCN),Clp]

giving

mainly

for the reaction

111301.

complex

given

reacted

[1129]. A range of catalysts

or [Cu(P(OCRHez}~Cl],

ratios in the products

palladium

I-ethenylcyclohexene

conditions

monosubstituted

on a

(419).

the

state

transition

[1132].

I

I

t

(419)

Pd Ctp /CuClz Op/dmf / l-420

1.10.5

Isomerisation

Ci#,trsns-1.5-cyclododecadiene in the presence have

been

of

used

PdCl,/CuCl to

(421)

isomerised

[1133].

catalyse

bicyclo[3.3.l]hepta-1,3-diene. intermediates

was

the The

Both

to

the

[Pd(PhCN),Clz]

isorerisation nechanisr

of

was

postulated

converted

to

(422)

rather

with

rearrangement

of

to

radical

almost

a vinyl

transfer

(reaction

(reaction of

process

was

(67)). which

was

chlrality

(88)) was

reaction

followed by attack

111351. A similar

rearrangement

complete epoxide

site

the

used

[1X361.

The

in synthesis

of

[1137].

Palladiur(I1) reviewed

at the less hindered

in a sulphinate+sulphone

accomplished

discussed

[Pd(nbd)Cl, J

involved

stereospecifically;

involved cleavage of the C-O bond to form an ally1 complex

pentenomycin

and

quadricyclane

[1134].

of the carboxylate involved

cis,cir-1,6-isomer

[1138]. [1139).

catalysed

[3.3]-sigmatropic

and

nechanisas

The

Cope

for

chiralfty

rearrangement

of

rearrangements transfer

in

have

such

(423) in the presence

been

reactions of PdC&

180 gave

B- and

X-isomers

of

(424)

in comparable

amounts

]1140].

0COR2

0

6

0COR2

R’

i F’c~(M~CN)~C~~]

(421)

Ar -S-OCH f .

(422)

RZ

2

0 R’ II z Ar-ScC-CH=CHZ

IPdWPh&1 -

(671

l

(68)

R’

WC12

R6 (422)

rearrangeaent

The

[Pd(MeCN),Cl,] X-isomers

hetero

ratio 30:70

of

of

more

stereochemical

(427):(428)

organophosphorus

a

(X = Me

to

in the (69).

R'

= Me

was

[3,3]-sigmatropic chemistry

[1143].

the

In

as

for

rearrangement

state

Me.

Reaction of

Rf .

p

of The

indicating

a

[1141].

by [Pd(PhCN),Cl,J.

R' = H or

[1142].

presence

intermediate.

transition

was catalysed

= H

an

the

B-analogues,

six-¤enbered

88:12

or R3

RHe,)

(426)

than

bias

obtained

or

involve

slowly

rearrangement.

= H or Ph.

of

(422)

postulated much

Claisen

for R'

example

was

reacted

considerable The

(424)

The

= Ii and

(70) was the first a

1. Seneyne

in

181

R’

‘x

Pd {II)

2J'NI-l

00

$

)

.



f?

R3

ll

. :

14281 c-. R3

Em,

,s (70)

The

of

use

derivatives allyiation

in using A

reviewed, ~1ladi~~KV) procass

orgaujc

cataiysed

synthesis

palladium

mechanism

or

nickel

rather

palladiurf0)

is quite convincing

uucleopbllfc

ha8

the

fO#?

intermediates,

involving

the arqutment

palladium

6nd

again

complexes

reaction than

the

substitution

been

widespread. as

catalysts

involvfnfg more

palladimm(II),

has

ally1

has

been

pal.ladium(II)

and

conventionally been

in terms of the system

of

Asymmetric

deecribed

proposed.

examined.

Mhilet

the theory

182 has not yet gained PhCH,ZnBr

reacted to

EPd(acac)o]/PPhs acceptable

organoretallfcs

and

but

catalysts

stereospecific reaction

via

[ll45jethanoate

ally1

other

PhCH,CH&H=CH,;

(11463.

The

various

ally1

compounds,

CPd(acac)z],

suitable

currency

with

give

results

Organoaluninium of

much general

R&Al,

yields

were

[1148].

The

the

well

in

ally1

derivatives with

geenerally low

known

of (421) was 83 % stereoselective

and

of

double

were

inversion

to

gave

various

examined

[11471.

in the presence

copper

(429)

of

also

of

PhSO,CH,CH=CHz

convkrsion

presence

reactivities

relative

reacted

the

derivatives

salts (430)

mechanism

were was

more fairly

[X149].

The

[1150].

COMe

&

CW20Si 83

Pi-6

rfWdppe~22 _

NaCti(COOEt)2

+

I

PhS

Me CH=C

p

I

Ar-S-O-CH, .:

/

\

[Pd(Pqh,) H + NaCH(COOMe),

al

Fe

(_I_LI_,

[Me0,C)+CH+CH=CH2

PPh3

t

83 t. 60 % ehirality

(431)

transfer

+ MeCH=CHCHzCH(C001Ye)2 50 4,

The been

regfocheristry

studied.

intermediate

r-ally1

using tungsten generally

Reaction

of

aliylic

generally

complex.

This

based catalysts,

yield

the

more

alkylation

occurs

catalysed

is in contrast

which

substituted

[Pd(PPh,),] terminus

to the analogous

are dominated

highly

by

at the less hindered

by electronic products

has

of the

reactions factors

(reaction

and

(71))

[1151,1152J. Tin enalates ally1 enolate

derivatives. of

generated

(433) in situ

Silfcon Me,SiSiMe,;

such aa

(4S2) have

generally (R = He,

proved

reacting

ally1

with

to be usefuf good

or CHzCH=CMez;

nucleophiles

regioselect~vlty 2 = 0 or q;

towards

111531.

The

n = 1 or 2) Was

(11543

substitution the yields

fn

an

of reaction

ally1

derivative

(72) depended

on

was

achieved

the catalyst.

using

R' and

RP

183 [11553.

mechanism

Although

reaction

is unknown.

(73)

is technically

intramofecular

a key step in the synthesis

allylic

FtNo

3

bl+

allylic

of depentylhIstrionicotoxin

COOR

Ph

an

substitution

Cow4

substjtution

(reaction

fts

(74)) was

[1157].

M=Pd -

I

M=W

\

The reaction of

of E-PhCH=CHCW&cCMe

E-PhC~~cHCH*cH*C~~

reeloaelectivity substrate

C1158].

of

the

and

with

alkynyltributyl tin gave a mixture generally the More

B-PhCH-CHCf(zCZf-C=Cfit.

reaction

depended

on

the

substituenta

on

the

ally1

P

+ Me3SiSiMe3

COR3

[Pd ( PPh314 1 or p [Pd (P(OPh13)41

d&me,

+

(72) RI&

SiMe3

t

Me3Si 0COR3

WC12 + A= CI

HOOH

(73)

%I

Cl

Treatment of the disubstituted

ally1 derivative.

of (435) and (4%)). The proposed

gave a mixture

(434), with a carbanion

reaction mechanism

is shown

in Scheme 8 111591. Diketene has proved a suitable substrate

g-RCH=CHA1(CH,CRMe2)+, Allenyl

Ill60].

R-CmC-ZnCl

derivatives

such

readily

reacting

[Pd(PPhS),Cl,l/dibaH.

of

presence

for allylic substitution

or

ArZnCl

to

give,

as

(439)

were

also

for

example,

readily

in the with (438)

substituted

[llSl] as were propargyl halides (440) 111621. 1.10.7 Coupling

Numerous

of

carbanlons

reactions

two reviews published by

KfCN)

reacted

in

the

vi&h

halides

of this type have again been discussed

this year and

[1163.1164]. Aryl halides were efficiently

presence

of

[Pd(PPhs),]

similarly and stereospecifically

and

18-crown-6.

[llSS]. Substitution

substituted

Alkenyl

halides

by NaCCH(CN)p)

was

also very

successful

[1166].

[Pd(dppfICl,] was the optimum catalyst the reaction of aryl or alkenyl halides with CH,CHpCH(MgBr)CH, fl1671.

for

14361

(435)

T

(43 7)

(437) Schere 6 Mechanism

of reaction of ally1 dlethanoates

UNe =

+ CR2Oaie

R/ZnCt

WWV’h3J41 -

with carbanfons

CllSS]

166

Me3Si \ Ph3Sn -

-4-

G

+

Me3Si -z

[ Pd (PPh3141 I

-2nCL

k +4 Ph3Sn

Cl

(4.40) Tin

derivatives

4-XC,H,I

have

(X = NO,.

being the

in

(Nu = OWe,

[PhPd(PPh,)ZI] presence

related

of

process this

(75)):

groups.

NEtz

or

tin

was of

only

presence R-R.

The

60

of

compounds,

was

reactions were

/\ 0-L

noted

“9R

+

of

(441)

of

[1170].

aryl

ring

electron

to

give

to

were

coupled

halide

useful

for

and

(442)

ion

with

aryl

suppressed

hindered (X = S

aryl or

halides

the

0;

of The

R = Br,

b

I

+

ArI

1)1Pd(PPh3141 2) MeOH

6COMe
the

[1172].

HgCl

0

in

formation

halides

N

A

this

(75)

cl

0

avoid

+ Bu,SnX

[PhPd(pph3)2’lt

&V

a

[1171].

X

HN

In

(reaction

Ar-Ar.

[1173,11743.

;a1

in

withdrawing

conditions

material

choice

MeOCH2SnBuS

yield

the

mild

catalyst

[1168].

'C

the

especially

good to

of using

alkynyl

with

bearing

starting

R,Hg,

[PhPd(PPh,),I]/I-;

reaction

in

rather

the

bromide

on

arenes

* ArSnBu,

mercury

predictable 2-thienyl)

with

+ ArX

Dialkyl

ArCHzOMe

catalysed

[Pd(PPh,),]. Bu,SnSnBu,

aryl

or the

reactive,

an

substitution occurred

alkenyl

substituted

under

with

palladium

of

gave was

conducted

being

also

Treatment

itself

ArSnBu,

was

Facile COOMe)

or

awl.

was

SPh)

successful

and

nucleophiles. COMe

R

[Pd(PPhS)2C12]

was

also

Cl,

which

[1169].

the

cross-coupling reaction

popular

CN.

RSnMe,/[Pd(MeCN),Clz] Alkyl,SnNu

been

NH3 6COM e

Cl

or

187 substituted

Nucleosides could

be

also

(TMSdR

C-5

at

obtained

by

in

a

carbocycle yield

low

,5'-deoxy-2'-ribose)

= O-trierthylsilyl-3'

or

by

heterocycle

reaction

(76)

111751.

0

0

Ar

I

H

fpd (PPh312C12 1 t

(76)

ArZnCl

c+Np

I i~sdR

;MSdR

reacted

[2,4.6-TrinethylphenylCuI] [PhPd(PPh,),L]

as

2.4,6-Me&aHzAr. withdrawing the

Aryl

groups

reaction

(76))

without

the

of

reported reagents

good

substrates.

nucleophiles

[1177,1176].

reactions

halides

were

transfer

phase

bearing

aryl

either

using

conditions

electron

although

iodide8

donating

very

strong

to

give

or

electron

donors

retarded

111761.

Organoborane halides

under

catalyst

with

need

have

for

with

have

of

+ Ar*rl

blso

[Pd(dppb)ClzJ

shown

to

complexes

reacted

(B(OH),)

Bromothiophenes

in the presence

been

to ate

halides

brorothiophenes

BEt2

year

conversion

Heteroaryl

[1179.1160].

this

react

(reactions

similarly:

substituted reacted

with

aryl

(77)

thiophenes

readily

and

several

with

new were

Grignard

[llSl].

Ar

Pd(PPh3)4E

cm

[Pd(PPhs I,] A~B(OH)

A been a

a + Ar'Br

number

of

reactions

A

reported.

synthesis

+ ArAr'

of

coupling

HCmC-C.H,-4-CICH

wa5

for

the

acieved

sytem

reaction, using

ArCmCCWeeOH. Ar' -CeC-Ar'

base ray in

reacted

a

but

[1184].

(reaction

one-pot

with

of

whilst in

a

HCeCCHzOH

gthyne

itself

ray

(79)) a

process

be

reaction

is not

situ

was

have

used

1.4-Cs&Xr

synthesis

in

with [1183].

[Pd(PPho)zC1z]/CuI/EtzNH a very

instead,

Alternatively

A

in

]/CuCl of

polymer using

equivalent

[1186].

formed

[Pt(PPha)pC1z

employed

[1185].

second

compounds

the

with

HOCMe.CnCH

react

copper

presence

[1182]. employed

also

the catalyst

alkyuyl

in the

carboranes

1.4-Diiodobenzene as

of

(76)

of

somewhat

suitable

substrate

deprotection the

initial

aryl

halide

more

unusual

being

product. to

give

reaction

188 occurred

using

mechanism

Br

the

of Scheme

xx

his

iodinated

9 was

proposed

H-s

as

(443).

the

I Pd(PPh3)$121,

The

Cul +

OH

COOMe

substrate.

[1187].

--c

COOMe +

biphenyl.

PPh3,

Et3N

(79)

HO

Numerous

alkenyl

heteroaryl

Grignard

stereospcificity reagents

in

selective

have in

was

the

Alkynylzinc

noted

presence

reaction

[Pd(PPh,),]

halides reagents

of

the

proved

useful

presence

of

reaction

[Pd(PPh,),]

of

substrates

reacting

with

[1181].

Good

[Pd(dppb)Clz] chloroalkenes

[1188].

and

(444)

with

also

Grignard

gave

a very

(11891.

reagents

to

in

also the

give

unreactive

was

E-ICH=CHCl

+ RCmCZnX

reacted

enynes

demonstrated

in

with

iodo

good

yield.

by reaction

or bronoalkenes That

(80)

in the

chloroalkenes

presence were

of

rather

[llSO]

CPd(PPh,),l

(Me3Si)3A1

reacted

X-Me 3SiCH=CHC5H2~ stereochemistry Two

applications

of

halides

the

generally The

articles the

E-

or

using

(80)

Z-C5HI,CH=CHI

[Pd(PPh9)4]

as

to

give

catalyst;

little

E-

or

loss

of

[llSl]. Normant's

from

cross-coupling

presence

excellent

of

of

group

have

alkenylcopper

palladium

described

compounds

complexes.

numerous

with

alkenyl

Stereoselectivity

was

(1192.1193]. of

alkenyltin

(OTf)

has

been

reaction

of

compounds

applied

to a short

with

alkenyl

synthesis

trifluoronethyl

of Pteraplysillin-1,

I11943.

In the complex

two

substitution only

observed

coupling

sulpphonates (445)

with

respectively was

lengthy

in

> E-ClCH=CH-C&R

outcomes of

the halide

the

(446)

with

could

be

haloalkene.

substitution

nucleophiles envisaged. In

practice,

occurred.

giving

in the viz. using (447)

presence

subatitution

allylic [PhCeC]in good

of a palladium

as

yield

or

nucleophile. [1195].

189

R

0’ Q-0 2

0

i

Ph-_,, PPh3

[pd fPPh&C12

1

cu2’2

i

(443)

R

OR Q-Q

R

0

I

L-RI

1

‘I R

Ph--

1

w

OR

0

Ph--=I$!

i

R

-0 9-Q

I

1-alkyne

9 Mechanism [1187].

SiMctOEt),

I-w-1 &II

L

Scheme

OR

of palladium

catalysed

coupling

of a diiodobiphenyl

with

a

190

OCOMe

b

OCOMe Br Ph--

+

I

N-methyl

pyrrolidone

(446)

(447)

Reaction

of

of

the

less

of

the

catalyst.

Thus

or

with

the

was

In

are

not

reaction

of

R'ZnX

groups.

this

A

Although

[1199].

aliyltrialkyltins depending

on

they

the

tin do

of

only

in these

in

context

precursor

with

react

substantial

processes.

conditions

1) 8ul.i

with

(81)

by the

behaved

have

other

synthesised

allylic

(reaction

2) ZnC12

reaction

proved

sensitive

in

reaction

transferred

from

transposition

could

was

group

absence

accelerated

nucleophiles

was

the

RR'C=CCu.MgX2

readily

pyrenophorin

derivatives

in

was

in

[1197].

containing

ally1

rapid

RCOCl

whilst

sifu

not

the

reaction

invariably

[1196].

generated

since

useful,

particularly

organometallics,

metals,

[PhCH,Pd(PPhl)&l]

[1196].

Punctional

occur,

halides

nucleophile

particularly

(62)

acyl

electropositive

IPd(PPh,) 41 organozinc similarly

0-l &

w (0)

(83))

[1200].

F

3~cH3cocl,~w~PP~3~2c125

Although additfon

a-haloketones

they

to palladium(O),

conditions

(reaction

a-haloaldehydes group

are

[l201].

since However,

(84)). the

tin

other

not do The

particularly

couple

with

reaction

nucleophile authors

.reactive tin

enolates

failed

for

attacked reported

towards under

appropriate

broropropanone

directly quite

oxidative

a

at

the

different

and

carbonyl process

191 (reaction

it

is

(85). n = 0, 1 or 2, R* = Bu. R' = ally1 or -CHzCOCH~) immediately

not

two

the

that

clear

observations

[1202] and

can

be

readily

reconciled.

Cl

+

BugSnW9”2Ph

[email protected]?

Y-pOSi Ph2CMeg

+C02CH2Ph

(82)

0SiPh2CMe3

R = Me.

[Pdtf’Phs)J.

65

50

56

Bu.

CPhCHpPd(PPhs)&l].

85 *

30

70

R = Bu.

CPhCHzPd(PPhS)&l].

50 -

fT

83

R

=

6u3Sn-fc + 6rIj<

(83)

[Pd(PhCN)2C121 (84)

-

0

0

l

0

1 PhCH2Pd

WPh312 Cl1 (85)

+ &If?;

In the presence

of

case,

cross-coupling

the

use

of

gave

reaction

ArCHClSfR,

undergo proposed

further

copper

the

initial

coupling,

(reactions

was

with Grignard

of PhBu was

and

(89)-(94)).

product an

employed

reagents

obtained

course

as

a

in this

resulted

in

more

catalyst

for

the

[1204].

the

(reactions

alternative the

catalysts

as

RsSiSiR!, In

of ArCifCl, with as

salts

[Pd(PPh,)&lp]

C12031.

coupling of iodocarboranes The

only a trace yield

of PhYbI and BuI; PhPh was the major product

from the cross-coupling although

[Pd(PPhs)r]

presence

palladlur(0)

(SS)-(86)).

coupling of

of

which

This

pathway depended

was on

could also the

192 substituents

[1205].

[PdL,] + ArCHCl, -+ [Pd(CHClAr)L,Cl]

+ R&i z w

[Pd(CHCIAr)(SiRS)Lt]

RSSiC1

[Pd(CHClAr)(SiR,)L,]

(87)

--_, (PdL,} + ArCHClSiR,

CPd(CHClAr)L&l]

+ Ar'CHCISiRS +

IPd(CHCIAr),La]

---c,ArCHClCHClAr

ArCHClCHClAr

(86)

[Pd(CHClAr)L,Cl]

(88)

[Pd(CHC1Ar),L2]

(89)

+ R&iCl

(90)

+ {PdL2)

(91)

+ [PdL+] --_* [ArCHCHCH(Ar)PdL,Cl]

CArCHClCHtAr)PdL,Cl]

w

[ArCHClCH(Ar)PdL,(SiR=)] ArCHC1CH(SiR3)Ar

P II_)

of

ArCHClCH(SiR,)Ar

(92)

+ (PdLz}

(93)

H-ArCH=CHAr

1.10.8 Oligomcrisation,

Dimerisation

+ R,SiCl

+ ReSiz --_, [ArCHClCH(Ar)PdL,(SiR,)1

(94)

tclomcrisation

ethene

Over

and

polymerisation

heterogenised

PdC12

[1206]

and

propene

heterogenised

Pd(CN)* have been reported.

The propene gave approxirately

linear dimers

E12073. The polymerisations

of phenylethene,

and bicyclo[3.3.l]heptene mechanism. with

Related

carbon

conditions

monoxide

to

[1208,1209].

methyl propenoate

Dimerisation with

polyphenylethyne

catalysed

complexes

give

The

of

an

same

to give (#8)

occurred

phenylethyne was obtained

by

alternating

catalyst

was

RCsCK,

to

give

in the presence and

by a carbocation

coplymerisation copolymer

used

73 %

1.3-cyclohexadiene

[Pd(MeCN)*]'+.

catalysed

under

in the

with 93-96 % selectivity

I-alkynes.

some higher oligomers, However,

were

phosphine

on

of alkenes very

mild

dimerisation

of

[1210.1211].

RCmC-C(R)=CHz of CPd(acac),

together ]/L/EtSN

with

C1212].

CPd(PPhs)rCl,]/PPho/CuI/EtoN/MeI.

[1213]. 3uteneyne

was readily cyclodimerised

to

193

give

although

ethenylbenxene:

the reaction

proceeds

increased in the presence of [Pd(acac),]/PPhl/EtsAl

theraally.

yields

were

112143. Polyuerisation

of

(449) in boiling pyridine or drf with PdClz as a catalyst yielded the soluble product

(450) [1215].

Telomerisation [Pd(acac),]/PPhs

dioctadienyl

the

arines

octadienyl

butane-1.4-diol

ethers,

which

between

of (151)

ammonia

and

were as

and the ratio of the products

the

starting

(12171.

aaterlals

monoxide.

and

the

used

presence

in

the

of

surfactant of aono and

catalyst

system.

could be controlled Wethanamide

yielded

by a

but in daso it decomposed

and <1;58) under these conditions, carbon

in

gave mixtures

[Pd(acac)zJ/PPh9/EtSAl

using

were excellent

ratio

mixture to

gave

with

112161. The 2-. 3- and 4-amlnopyridines

synthesis Yields

butadiene

of

the ammonia

telomer,

~ltls

4-1.

also

formed [12f8]. NHCHO -NHCHO

(452)

4-11

Reaction

of butadiene

rIth arylsulphinic

acids.

products, depending on the exact reaction conditions Telomeriaation gave a-octadienyl

of

butadiene

ketones.

with

Little of any branched

to 30 X of the 2,2-bis(octadleny1) product the

ratio

same

teloner,

depended

reaction was

the

the enolate

primarily

product on

was

considered

major

product.

considered to be [HPdLIJIOH]

[1221].

for

cyclic

cases

ketones

product was formed. but up in some cases.

of the phosphiae

isoprene.

both

of

[1219]. ions from

was produced

the bulk

In

(454). gave mixtures

I=). the

the active

The

[1220]. When tail-to-tail catalyst

was

194

3!” R’ 0

[ PdL,l

+ H---d=-

i-

+

R2 (454)

In a novel and unusual process Me,_,X,SiSiX,Me,_,

reacted with butadiene

or isoprene to give (4b6) (R = H or Me) using Pd(OCOMe), catalyst.

A complex mechanism

explained

carbon dioxide and butadiene. palladium(O)

of PEta or PBu,

cyclopropane

Investigated. be produced

the formation

with

of products

[1222].

(457)-(461)

from

Up to 95 % of (457) could be obtained using the

complex of a bulky phosphine

use of complexes methylene

or [Pd(PhCNh Cl, ] as

(456) (R = H) was used in a short synthesis of muscone

CO2

gave t-1 in

the

of high basicity presence

Lactonea were the invariable products. in up to 80 % selectivity

by judicious

complex mixture of products more generally resulted

such as PCy,. The

112231.

or (461) of

The reaction of

[PdLI]

has

arid although choice [1224].

also

been

(462) could

of conditions,

a

195

b-0 0

Oxidative Routes

dimerisation

involving

distinguished

112251.

rate-controlling

dimerisation R’

a

or

El

strictly

In

step

and

the

was

The reaction

intermediate.

of toluene using Pd[SO,]/Hz[SO,]

palladium(I)

oxidative

said yielded

to

be

was

catalytic

achieved

oligomerisation Pormation

using

(46S)

15-71

(464)

gave

with

as

a

mixture

palladium

[1226]. Oxidative

the

reaction

NQ ,

was

not

HgCl

RR-;

[Pd(PPh,)*J

Li.+WCl41,

[1228].

of

gave only the E.&product

r:

but

the

O/o

of 4-bromothiophenol (465)

condensation

aryl

be

, Me COOH

para-polyphenylenethioether

gave

benzene

(X = 0 or S. R = MeCO. MO.

Pd(OCOMe)t.

)

Me3COH

the

could

[1227].

Pd tOCOMe

Treatment

of

of

2-. 3- and 4-terphenyls

of furans and thiophenes. Me).

has been studied.

intermediates

palladiua(II)

E.Z-

in a mixture

Oxidative

and

of BuOH and

dimerisatfon

Z,Z-isomers.

The

of

Stobbe

112291.

CuClq

COO H

Ar

COOH (4-1

(4651

Platinum(I1) catalyst

for

boron-boron

bromide

boron

was

hydrides

linked polyhedral

shown and

to

be

carboranes

cage compounds

a

general leading

dehydrodirerisation to

the

Pormation

of

in good yields and selectivities

196 under

mild

mechanism

conditions

(for example,

reactions

is not known with any certainty

was found to depend on the electron was proposed

(95) and

(96)). The

reaction

but since the site of the coupling an initial electrophilic

density,

attack

[1230].

Pt3I-z. 25 'C 2B5Hs

*

1:2'(B,H,)z

(95)

B

l:l'(BhH,)t

(96)

PtBrz, 25 'C ~B,RI,, 1.X0.9 Other

Again synthesis

coupling

the Heck

shown

reaction

this year

of aryl halides

aryl

reactions

have,

in Scheme chlorides

10 have

and

related

(for example, however,

been

The

published

first using

other reagent, but yields were In all cases

been widely

(97)) 112311. Reports

been much more

[1232-12371.

have

processes

reaction

nuaerous,

reports

examples

some

of coupling

phenylethene

or

used

in

of couplings being

reactions

CEIL-CHCN

as

of the

low [1238-12401

(97)

Pd(OCOMe) 2/Na[HC0~]/[Bu4NIC1 5 El-PhCH-CHCOOMe

Phi + CH,=CHCtlOMe [Pd(OCOMe)p(PPh,),]

, ArCIi(R)CHxCHO

ArI + E-RCH-CHCHO Br

+

Pd (OCOMe12,

NaOCOMe

fiCONMe* P(C6H4-4-MeI2

CQOH COOMe

ArBr

+

COOH

===c

Pd(OCOMe)z

cool-l PP$,

RsN 9

ArCH

Scheme

10 Heck reactions

of aryl halides

4 NHCOMe

NHCOMe

[1231-12371

198

Several with

or alkyl) at

papers

alkyl

the

have reported

propenoates. but

the oxidative

(466) coupling

if this site was blocked,

2-position

similar

For

[1242,1243].

conditions

coupling

occurred

as in(ltf7).

Furfural

of indole derivatives

at the 3-position

reacted

substitution

at

the

(R = H

took place

5-position

under

112441

CXA, + I

kOOEt

doolEt (466) Pd (OCOMe12 t

ACOOEt

-

I

COOEt

MeCOO H v

COAr (467) Diphenylethyne

reacted

with

iodabenxene

[Pd(PPh,),(OCOWe)t]/HCOOH/EtSN/MeCN

to

rechaniam

oxidative

was

followed

by alkyne

Addition catalysed

of

by

R' = Ph.

involve

C,HIJ

with

electron

compound, (reaction

or

C,HII) but

aldehydes.

Zn.

withdrawing

The

metal complex

of

the

of

reaction

aryl

halide

formed

in situ.

Organotin

[1246].

group)

be

induced

using

to

[PdLZClz]

a rather

to an

aldehyde

n = 0.1.3.5

compounds couple as

low optical

do

with

occurred a

Cyclisation

coupling

not

in

ArCHO

catalyst

(Ar

(reaction

yield was obtained

(QQ)

of

1

ArCH(OH)CH,CN of

organic

in the presence

palladium

mixture

was

or 7:

> RCH(R')CHO

reductive

and

addition

The

CPd(PPh3)+C121

CPdLtClt + ArCHO _____)

hydrazine

presence

112471.

RI + R'CHO

Bu$SnCH&N

the

(99) R = (CF,)&Fg,

may

(100)). When L was a chiral phosphine for this process

in

triphenylethene.

[1245].

organoxinc

(Pd(PPh9)&lZ]

react an

to

insertion

an

PhCH-CH-,

general bears

thought

give

complex

(100)

halides

of

the The

hydraxine

of PdCl= or PdCll/HgC1,

as

catalyst

the

RIR1. R*R', RLRz, R'I and R21

[Pd(MeCN)&l,]/WeCOOH.

using

enyne, mechanism

t-1. of

salts

or

an

[1248]. Using [R'R*I]X

aryl zinc

yielded

a

[1249].

occurred the 'reaction

in

the

was

not

presence fully

of

defined

199 but

and

palladiur(I1)

could

intermediates

palladium(IV)

be

postulated

[1250.1251].

B

R’

OcMe

4

[RJ(MeCN12C12~,

MeCOOH

R2 (488) Reaction

of

[Pd(PhCN),CIZ] arylated [1252].

ethanoate.

Grignard

the

catalyst

as

alkenes Low

aryl

and

yields

CH~C(OCOMe)=CflZ.

[Pd{P(2-MeCsH4)9}2C1z] halides

also

to

nixtures

well

as

a

obtained

in

reaction

with

reacted

give

yields

which

low

amount

(101)

IBu,SnOMe

dienes

with

substantial

Bu,SnC&COMe.

in modest

to give ArCHzCOMe

substituted

with

complex

gave

as

dienes.

were

reagents

yields of

[1253]. the

in was

using

biaryls The

enol

presence

coupled

of

of

with

aryl

[1254].

[pd (acac121 PhMgBr

Two reactions

+ PhS02m

>Ph-

lethylations

new have

been

of

reported.

2.6-bis(l.l-diaethylethyl)

rings

aryl

of

reacted with methyl collapsed

phenol

PhNHCOCH,

with

palladium

methanal/H,

93 x

gave

intermediate,

PdCl,

to

selectivity

ethanoate

iodide to give a palladium(IV)

catalysed

supported

give [1255].

(439)

which

(470). which

to (471) [1256].

(4’10)

Coupling presence

with

with palladium

(101)

of Amberlite

reacted

t-1

X-ray

involving

In the presence

2.6-bis(l,l-dinethylethyl)-4-methylphenol Cyclonetallation

+

of

of

I-bromonitrobenzene

[Pd(PPh,),]

diffraction.

gave

a mixture

The mechanism

with of

(471) bicycloC3.3.lJheptene

(472) and

was not defined,

in

(473). characterised

but uaa thought

the by

to involve

alkynes

112571. Bicyclo[3.3.l]heptene

intermediate

an aryne

via the mechanism

of Scheme

11 to give cyclopropanes

R’+

with

dialkyl

[1258].

(473)

(472)

R-E_

also reacted

~(0)

+H+

-

R’-CH

=CR

-

65/ ,

Pd+

I

Pd

Scheme

cyclopropanation

catalysed

Palladium

11

bicyclo[3.3.llheptene

of

[1258].

Electrophilic ethanoate

gave

substitution

(475).

Other

Hexaalkyl could

reactions

ditin

be converted

cyclometallation

of

(476) was formed vie a palladium

Indoles were synthesised

1.10.10

and

by reaction

catalysed

compounds to R'SnR,

by

were

shift

palladium

[1259].

(102) [1260]. and

palladium

prepared

in reaction

(474) with

platinum

by reactions

(105)

corrplcxes

(103) and

[1261]. Hydrolysis

(104) and of ArSiMeo

201 to

give

and

MelSiOSiMes

rechanism

of

the

ArH

reaction

were

key step was electrophilfc Treatment

of

H,[PtCl,J migrated

catalysed

substitution

LiIIPdC1.]. and

it was

The

kinetics

concluded

trichlorosilane

In mixed

and selectivity

silanea

in

the

good

the

[1262].

presence

the least hindered

was generally

and

that

of the aryl ring by palladium

with

and RSiHC12.

the most easfly.

by

investigated,

sflaues

tetraalkyl

gave R,SiCl

was

of

groups

[1263].

Pd (OCOMe I2 + R (4741

(4761

Li2ZIPdC141 +

3

-r=sS3\0CONe

mx?!l

(163) R,SnH

+ Pd(0)

--w

R,SnPdH

--M

R,Sn,

+ YHp + Pd(0)

(104)

fPdOIeCN],Clzl/hmpa w R'SnRI

R'X f R,Sn, Rydroailylatlon with

added

aaine

(477).

Enantlorer

alkyl

silanes,

catalyaed

by

of

ketone8

chelate

RSiXl.

occurred

ligands.

excesses

were

In

and also

rodest

(1051

the

presence

using

in nost

isolated

cases

x,3,5-trihydroxybenzene

with

[Pt(PPha)&lz]

+ R,SnX

or

Wz[PtCle].

but

better

of

complexes

[1264]. to

KIPt(CzH,)Cl,] such

Condensation give

yields

were

(478)

as of waa

obtained

202 using

[Rh(PPh3)&1] of

presence (reaction

[1265]. Reaction

[Pd(PPh,),]

gave

(106)) the ratio between

conditions

of a-haloketones

sibyl

enol

ethers

the products

with Bu,SnSiMe3

and

in the

dehalogenated

depending

ketones

on the catalyst

and

[lZSS].

(479)

(477)

tPd(PPh 3) 41 + PhC(OSiMe3)=CHZ

+ BrCH,COPh

Bu,SnSiMe,

A patent

has reported

an ester in the presence presumed Ally1

to involve

complex

in reaction

the catalytic

formation

(reaction

carbonate

intermediate

an enolate

to give

to

(107)). The process was

of a n-ally1 palladium

and decarboxylation

(106)

of an ally1

conversion

of carbon monoxide

carbonylation

+ PhCOMe

112671.

was

involved

(108) Il268). Pd(OCOMe)z/PPhS/CO d CHz=CHCH,COOMe

CHZ=CHCHtOCOOMe

Pd WOMe)2

,dm=

(107)

~

MeCN 13'10

65 %

(108)

Alkenyl catalysed In the

esters

presence

carbon

supported

carboxylic

transesterification

with molecular to

of

of

acids

could

with ethenyl ethanoate

[I%&]'-.

[PtX,12-

or

monoxide

and

hydrogen

Pd(OCOMe),. K[OCOMe],

of

occurred

by

(reaction

(109)) [l269]. ethanol

[1279]. Conversion in

the

palladium

presence

reacted

of methanol of

Hz[PtCle]

(12711.

EtCOOH + CH&.H=OCOMe

Quaternisation

prepared

trsns-[Pt(py),XZ]

iodine to give ethyl ethanoate

on AJ,03/Ce0,

be

Cu(OCOMe)l

) KBr. 48 hr, 60-C

triarylphosphines

with

EtCO&H=CHz

aryl

halides

(199)

was

catalysed

by

203 CPd(PPh,),l hindrance

or [1272].

of triaryl

Cleavage

using palladium(I1) migration

reaction

the

Pd(OCOMe),;

ethanoate

was

quite

phosphines

sensitive

or stibines

The reaction

in toluene.

of an aryl group from phosphorus

to

steric

occurred

slowly

was thought

to involve

(479) (12731.

to palladium,

(479)

Intramolecular reaction from

(110).

substitution

However,

cyclisation alcohol

catalysed

cyclisation

probably of

an

isoaeric

geometric

by

propargyl

the

of

iodide

substrate,

factors,

acting (481)

aryl

as

was

the used

by

underwent

a

which

(480).

reductant in

oxygen

occurred

is prevented

hydrogenolysis, C12741.

synthesis

of

in

The

the

palladium

lavendamycin

[1275].

Pd (11)

-OH, %@ Cu(Il)

[email protected]

-OH,

Cu

(1101

Et3N

(II),

Pd (11) > Et3N,

81 V.

--‘2; 0

Cl

IN---OH Cl

0

Treatment PhCN)

at

of

180 'C

a

primary

for

5

amine,

hours

gave

RNHz.

R,NH

with by

[PtL&lz]/SnC12 an

unknown

(L = PPho

mechanism

or

[r276].

204 Reaction

with

Na[OMe]/MeOH

of

C((n 3-allyl)PdCl)t]/Bu3P

MeOOC

gave up to 46 % methoxy

isoprenes

of

[1277]. COOMe

H2N Br

J,

80 ‘C

thf

Treatment

of

(X = Cl

(482)

Pd(OCOMe),/PPh,/Na[OCOMe]/hydroquinone studied

accomplished catalytic

presence

the

in

COOMe [Pd(PPh$4

not

isoprene

112781. using

gave

Dehydrogenation

of

with

OCOMe)

OX-

(483); the reaction mechanism RCH-CHCHO RCH&H&HO to

Ag[OSO,CF,]/[Pd(PhCN),C1,1;

the reaction

was

not

was was

strictly

(12791 X

\ pd (OCOMe)2,

PPh3

NaOCOMe hydroquinone

(-2) The opening an effective

of the epoxide,

synthesis

the aore stable

of

conformer

(484). was rather

chlorodeoxy

sugars.

of the intermediate,

regioselective.

The

product

(485) [1280].

1

R2 I HOQb

R’ OH

was

leading derived

to

from

Kz[PdCl,l

on

supported

copolymer.

polystyrene-divinylbenzene hydroperoxide

to cyclohexanone

of CH,CH,CH&R=CHCHO

species

diagrams

and

RbC1.3PdClz melted for

phases

Li2[PdC14]

The

interaction bismuth

redox

reactions

palladium

281

+

Studies platinum

by

by programmed near hexagonal

[1286].

a

gave

cyclohexyl

a small amount

melt

Zn*+

LEBD,

+

Auger

oxidation

heating

under

centred

ionisation were

to

melt

stepwise

below

and

were

Phase phase

observed.

and CsC1.3PdCb also

constructed Type V

351 'C. NbC15/PdClz

containing

the

[1282].

X-ray were

the Roozeboor

and

is of the

at 197 'C [1284].

NaCl/CsCl

in the temperature resulted

energy

observed

region,

diagrams

solid

congruently.

MC1.3PdClt

is of

their

in

I*elt (35:65)

range

the

791-1073

complete

with The

K.

transfer

of

[1285].

+

3Pd

(ill)

Pd

(112)

spectroscopy surfaces,

and

Prhich had

and reduction, an argon

adlattice

platinuas

Phase

phase

(112)

and

thernogravimetric

LiCl/PdCl,

studied

monocrystal

and five

shown

composition

112831.

palladium

2Bi"+

II_+

decreased

at 96.5 mole % NbC15

and

-



adlattice

of

(111)

by electrochemical

iodines

DTA. the

in the solid

to the metallic

Pd'+

At

were

with

system.

or zinc was

3Pd2+

+

with

Pt.Cl12

fPdxPte_&ll,]*

from

type with a eutectic

liquid

PdoCII,,

50 eV. and

at 361 lC

the PdCl,/LiCl/NdCl,

contained

of

COMPOUNDS

above 340 lC in the subsolidus

decomposed

incongruently

eutectic

Zn

New

on

Csz[PdCld]

constructed

data.

at

fPtsC112J+

tetragonal

were

analytical

together

a

Or‘

17 clcmcnts

fragmentation

[PdeClltJ+.

Rbr[PdClb]

and cyclohexanol

measurements

spectronetric showed

conversion

catalysed

BINARY AND TERNARY

1.11.1 Compauoclw with Group

solution

Amberlyst-27

1.

[1281].

1.11 NON-STOICHEIOMETRIC.

Mass

Dowex

electrochemistry been

were restored

atmosphere

containing

unit

iodine desorption

cell.

Progr%mred

and a series

iodine

state

vapour.

containing heating

of related

that

disordered

to an ordered

of iodine atoms was formed.

per surface

showed

deliberately

A

three of the

adlattices

206

1.1X.2

Compounds

The

structural

oxides

have

solid

PdO

been

higher

energy

calculations finite

XPES

data

transition

XPES

different

in

supported XANES Prom

inert

spectrum the

local the

on

analysis

unoccupied PdO

catalysts

dissolution

studied

to detrmine

support

[1293]. of

Ptoz under

equilibriur a

40-60 kbar and

from

PdO

an

edges

each

were also consistent catalyst

the platinum to that

by

not

be

X-ray made

mite

by

support

was

did depend

PdO

PdO

line

"p-like"

The

[1291].

catalysts in the

was

molecular

reported

M

HCl

the

rutile

shown

to

have

structures

or at

on

the

oxygen

near

for 8-PtOz

and

of these compounds.

neighbours

It was

HICIOS]

Na+[Pt(OH)s].

six

Data

gave

structure

measurements

and 8-PtOz,

was

on the

oxygen

of cc-PtOz with

of

structural

for

in 0.2-0.8

absorption

six oxygen

energy. "d-like"

of the PdO catalyst

with

PdO

structures

Evidence

in a-

was

and

local

the CdIn structure.

of =-PtOz.

produced

obtained

interactions

l!3'-PM12 with

with the known had

could

the

study

alumina

platinum

platinum with

wave method

anhydrous

to

the

11801. Treatment

been

used

experimental

state with 0.8 eV binding

crystals,

of

with

with

The

the dispersion

of

have

In Adam's

similar

A

to

workers

supports,

from

used

determined.

suppoorted

filament

at 2.05 A. consistent

structure

of

that PdO.nl$ 0 was not very

energy

L1

590 'C f1294].

In a-PtOz

assigned

Soviet

of the species

and for PdO.substrate PdO

edges

gap

d-d transition.

structure

interaction

also

and were

conditions

and

LIII

band

was

compared

various

substrates.

states

Li0_aPt304 edge

was

L3

modification

pressure

LII and

Li0.BPt304+

neighbours

new

and

[1290]. on

binding

the

a glowing

a

the X, scattered

were

it was also noted

quantitatively

BaOp

platinum

of

of

of

of PdO have been

with

2.2 eV

platinum

formation

electronic

crystals

electronic

The

quasi-inert

differed

The

gave

the

PdO .nHIO

radiation

catalysts,

112921.

Reaction

that

but the nature

electronic

in these

of

The

studied.

model wIthin

The results

Pd 3dSjz

and

been

was found to be an excitonic

joint

disorder

has

treatments.

of

ternary

forbidden

near

Field theory

study

synchrotron

single

semiconductor

PdO

of the support.

terms

using

and

energy

[1288].

to a strongly

cluster

found to be weak,

on the activity

XANES

to

grown

threshold

concluded

impregnation

generally

a

of

by simple crystal used

free

[1289].

conditions.

it was

was

different

with

on a [PdsOs]*-

and

of binary

standard

p-type

structure

boundary

interpreted

a

charge transfer

electronic

with

of vapour

was

9.8 eV. corresponding

0(2p)-Pd(4d) The

PdO

The

electrochemically

propoerties

This

properties

[1287].

determined

electrochemical

approximately

16 elements

and electronic reviewed

was

reported.

Croup

with

concluded

at 2.06 A and that

this

was

an a

207

highly

disorded

Single platinum

be

a

of

for

greater The

of

in the to

from

showed

group

hydrolysis

than

In,O,

(25-30

the

symmetry

was

[1298].

[PtMoaO,,]e-

obtained

sample

%)

and

material

having

was

shown

2ma(C,,)

electrode

media.

ideal

was

two the

firing

%)

to

specific

a

form

surface

obtained

was

An

X-ray

Anderson

type

to

X-ray

geometrical other

diffraction structure

at study

with

analysis.

one

same

having

framework

the

as

the

examined

in

[1299].

its

and

were

the

i&d and

diffraction

isomers.

with (487)

prepared AS'

of

found

K3.sCa-H1.SPtMo~O~,l.3H~0

symmetry,

AH’ and

aG*.

an

subjected

have and

(486).

ion and

Pt/PtS

to

In

(0.06-5 a

and

were

[12943].

PdO

SrO

[1297],

compounds were

of

a structure

crystals

KaNaz[PtW60z,].12Hz0

had

The .l.5H20

structure.

heptamolybdate A

(75-50

reaction

revealed

Single

a powder

raw

derivative,

heteropolyanion

[NH,J,[B-H4PtMosOz4]

different

a

the

R&(167).

SnO

X).

gases,

25 mzg-'

from analysis

K,~WO.~.2H,O/K,[Pt(OA),l/Na~/HfNO,J.

that

Anderson

obtained

diffraction

space

heteropolyanion

pH 7.5

were

Sr,PtOs

combustible

than

112951.

'C. X-ray

1150

resistant

mixture

detector

area

at

symmetry

more

powdered

of a-PtO,

crystals

metal

rhombohedral to

form

behaviour

determined

for

was

the

equilibrium

(113)

c13003.

Pt(s)

+

4

S'Taq)

The

species

powder

diffraction. curves under

of PdSe

A

in such

NbzPdlSe..

types

The X = P,

prisms

structures

distances

or were

S)

system

typical

the been of

showed

halogen

solution

completely

15

the

revealed

with

"Tunnels"

Croup

of

studied

by

loss

were

X-ray [1301].

plotted

Electrochemical

and

by niobium.

one

on

a

decomposition

under

the

existence two

The

square

along

semiconductor

have

hydroxide

analysis

centred

coordination.

As

towards

conditions. rapidly

were

conditions

in

[1302].

atore,

with

PtTe,Cllt

unstable

sodium

oacurred

diffraction

a metallic

Cowpaunds

in

Nb/Pd/Se

palladium

was

1.x1.3

the

trigonal of

pyramidal phase

occurred

of X-ray

selenium

PdSe

and

rather

potentiodynaaic

solutions

oxidation study

were

for

(113)

PtSezCltz

All

Polarisation

2e-

+

PtSe,Cl,.

potentiostat

which

PtS(s)

of

chains

chains planar

a

of

new

edge-sharing

conjoined and

c-direction

phase,

through

one

with

resulted

two

square and

the

[1303].

elements

species studied. single

4EM+ In

bonds,

(A = K.

KpPdA+ whilst

Na

or

and

&PdPz

the

Pd-Pd

Rb; the

M = Pd

or

Pt;

As-As

and

P-P

distance

of

3.01

A

implied in

some

terms

planar

PtSz

analysed planar

of

interaction. a

puckered

chains.

in terms

chain

The

of the

but

fell

of a full

one-dimensional band

structure

increased

into a zig-zag

ribbon

(486) (Reproduced Structure

short

chafn of

these

stability

bond.

This

structure. species

afforded

was

explained

KZ PtSz

was

contains

calculated

by the bending

and

of the

[1304].

with permission

from

[1299])

of IJS-H.PtMo~O,.]~- anion (H atoms not shown) and its polyhedral model. * = protonated oxygen atom.

209

otz1

Ot18

(487) Structure

(Reproduced

of [a-H4_5PtMo0z4]3-Spolyhedral

The compounds HO,

Er or M).

elements.

MPd.P.

L%PdeP17

Guinier

respectively

with permission

CeMgSi,

type structure

showed

structural

anion

(W = Ca. Sr, Y. patterns

However,

indicated

of

the

oxygen

and its

atom. Sm.

Pr, Nd,

been prepared

Eu, Gd, Tb, By.

by reaction

ThCr,Si t and L+Ni,P,,

and

but had tetragonal

elements

La, Ce,

have

BaPd,Pz

[1299])

(H ators not shown)

* = protonated

and CesP&P17

powder

[13OS].

model.

from

BaPd,As,

symmetry.

CaBe2Gez

Some

type

structures

crystallised crystals

[lSOS].

of the

of

in

the

BaP&As,

EuPdrPz

was

210 previously cell

classed

volume

anomaly.

measurement anomalies ligands

as an intermediate

have

data

platinum

the

on

site

and

binding

was

and

on the basis magnetic

europium(I1) bonding

two

with

of a unit

susceptibility

derivative

between

In

distinguished.

data

with

to

The

and

Eu(I1)

by

reaction

characteristics of thin

the

and the

treatment

in a hydrogen

The palladium

was

30-40 c1 cm-' was

PdeP

also

was

classes

isotypic

with

permitted

UU2

of neutron previous

PdePD0_26

have same

the

solutions

in PdeP

.by hydrogen,

of

phase

silicon of

with

produced

GaAs.

and

and

like

with

followed phase

PdAsz

phase

NbBA = 3

to 5

on

and

the

on

the

electrochemical

by palladium

analysis

layers

and SIMS

interdiffusion and

be

electron

treatment

interface,

gallium

Pd,Ga,

could

valence

by successive

X-ray

palladium

phase

a post brass-like

thermal

or arsenic

compounds

atmosphere

At

occupy

occupied

metal-semiconductor

of contacts

of

[1308].

with

and

deuterium

per

PdGa

were

and

the

under

thermal

coupled

devices

[1312].

and PtSi

in Schottky

barrier

IR charge

113137. of

[1314].

layers

rate

Pd,PH,_,,

the

holes

silicon

of PdzSi

synthesis

investigated

and

brass-like

of n-n+

also sites

[1309]. Comparison

three

phase

the

intermetallic

with

It was atomic

and

were

5d

platinum

in PdePo.,,. For

investigated

process

of

The use

final

structure

has been reviewed

a

pure

of

of

[lSlO].

layers of gallium

formation

Compounds

site

number

PdlP0.BD0_15,

hydrogen

system

at

deposition

the

phases

Pd,Po.sRo_l,

deuterium

was

electrical

study

and

dissolved

was

3. The

the epitaxial

composition

structure

NbpA = 1 and 2, and the second

effect

physicochemical

to

when

for PdP.

that

first

The

between

than

The

with

for PdsPoae.

one additional

concentrations NbQA = 2

greater

for

NiPd,,,As,,,ralloy

the

[1311].

data

near-in

published.

that of related

occupied

occupied

been

electron

positions

sites

hydrogen

absorption

be

supposition

the

crystallographic

growth

a

chemical

in equilibrium

structural

diffraction

confirmed

to

was

compatible

neutron

1.X1-4

strong

have

shown

its valence

diffraction

used

shifts

it is

X-ray

systems

'C Pd1_5C~1_5P

Pd,Se,

on

isomer

that

compound

[1307].

(NiO_5PtO_5)75PZ5

the

proved

may be attributed-to

New

500

MlSssbauer

now

valence

has

PdzSi

formation

been

studied

found

to

obtained

over a few seconds

films

The

be

via of

source

dual

PdzSi

by

as a function

diffusion

for ZOO-400

[1315]. The process

rapid

sputtering thermal

of annealing

limited.

A

nr thick Pd&i was studied

silicide layers by mass

has

been

annealing time,

of

and

the

resistivity

of

formed

at 400 'C

spectrometry.

and

211

Epitaxial became

growth

deposited face

At

with

fror

strong

a

saturated

characteristic

metals

of

photo-emission

studies

Interdiffusion

in

studied

using

to diffuse accumulated PES

at the

and

Pd/SiC

EELS

dissolved

On

carbon.

annealing oxidation

The PdSi, the

of

PtzSi

(sic).

The

of metal

was

were It

used was

been

Pt/Ni

using

and to

on uaed

silicide

Auger

identify that the

the

metal

up. was

phase

by

by

and

silicide in the MeV

Ni-Pt-Si

studied

system

present starts

contact the by

at

film

form and and

a

113201.

systems

Nickel

and

was

upon

was shown

which

oxidation

room

silicide

on

the

of

temperature,

it

silicon of

proceeded

by

Si(Si20+).

some

coverage

than Pa Si.

sites

[1322].

Pd,Si,

PdzSi,

chenisorptlon

Si(SiOs)

increased

the and

and

palladium

oxidation

thickness

with other

sputter

as

a function

spectroretry, (AES).

spectroscopy

metals

Subsequently

a

radiation

Pd,,Si rather

and

Growth

backscattering

reaction in

Pd,Si

Si(Si,O).

film

was

with

and the

at SiOI

amount

[1323].

electron the

PES.

of

to

silicon

PdzSi.

dependence

of

temperature

by

change

calculations

palladium

preferentially

studied

temperatures

The

electronic

(RBS).

at

of

lineshape

formation

localisation

value

thin

formation

consisting

room

magnetic

synchrotron

and

reactive

presence

positive

[1321]. the

was

a

lower

The

of

[1318].

high

between

polycrystalline

observe

oxidation

formation

shown

depending has

of

initial

investigated

diffraction

was

with

degree

in the

Silfcide

films

PtSi

atoms

to

occurred

oxide

and

silicon

by

spectrometry

of

interface

the

at

bulk

interface

silicides,

scattering

Si(L,,,VV)

implied

adsorption

growth

its

[1319].

the

formation

two-dimensional

investigated

interface

surface The

time

at



showed

I\)

in field

from

film

occur

boundaries

used

The a

of

scattering

bulk

back

grain

were

gave

(6-55

logarithmic

a silicon

interlayer

At

Si/Pd,Si

interface.

intermixing

and

the

Pd/PdzSi

silicon were

that

the Cu/Si

Si/Pd,Si/NiSi/Pd,si/Ni

Rutherford

along

tbe

showed

of

palladium

on

value.

been

of

the

copper

scattering.

which

have

of

independent

two-dimensional

variety

of

a field

a

of

of

temperature

segregation

spin-orbit

spin-orbit

interactions

layers

formation.

room

to

of

morphological

at

coverages

results

was

silicide

formed

Surface

'C.

characteristic

(three-dimensional)

crossover

of

which

being

P&Si

presence

films

during

Various a few

by the

ultrathin

phenomenon

200

Photoemission

magnetoresistance

this

to

formed

silicon

113161.

at

[13173.

inhibited

K

'C

300

'C

temperature.

1.3-50

for

annealing

magnetoresistance

due

at

400

strongly

anisotropic fields,

after

substrates

room

was

noted

above

en

at

Pd,Si

the

was

epitaxial

observed

was

observed

was

separation

isotope

at

the

with

metal

of all

diffuses a

treatment

barrier

silicide/silicon

until

depositing

heat

glancing-angle

Schottky

formation

silicon,

of

600

113241. A

interface.

NizSi the

X-ray values

or

contact

PtzSi. metal

Formation

Pt_4Nbmrr

of

alloy

212 layer

on

to

300-750



'C.

n-type AES

RBS.

characterisation. structure, result. atom

The

and

The

only

A

platinum

crystal X-ray

silicon.

reactions

"as

phase

and

was

films

stable

this

phases.

Pt

and by

a-PtzSi

proportional Raman

using

the

by AES;

The

atomic

platfnua platinun interface the

a

and

tunnelling found

different

few

and

had

the

enrichment and

the

in a

[1332].

The

on



1.3

PtSi

eV

field

ion

found

the

layers

including grow

Beyond of

perfection

PtSi/Si

silicon

silicide

tens

were

The rate

The the

[1330].

The

films

w%s

grown

on

near

relatively layers

epitaxial

lattice

image

domains

described

layers

atomic of

Si

[1331].

layers

were

with

a

the

P&S1

interface

substrate.

lC.

with

on

and

microscope.

PtzSi.

still

Irm

used

investigate

technique

observed

of

couples were

to

PtSi

was

film

mixtures

[1328].

of

(AIBE)

films

400-700

formed

of

(TEM)

PtSi a

alumina

PtSi

crystalline of

microscopy

epitaxial

were

of

to

diffusion

4-30

of

crystalline

due

on

of

composition

atoms

Lateral

composition the

thicker

platinum

patterns

and

interface

of

40 k

of

were

chemical

the

35 I\. With

length

etching

A

with

characteristics

beam

films

nucleation

layers

identify

involving

obtain at

measurements

energy

to

than

by

in the

structural

to

range

a

analysed

lo-60

for

temperature

composition

microstructure

positions

used

ion

studied

silicon

over

Etching

on

structure

the

an activation been

assisted

platinum

electron that

has

silicon

single

species

range

and

other

microprobe

over

grow

to

113271.

on

electron

[1329J.

were

interface

and

mobile

formed

less

and

metal

leaving

in ultra-thin

was

substrates

phase

platinum

nechanisr

profiling,

respect

islands

to

boubardaent

matrix the

the

silicides

(time)*

interface

platinum

films

was

surface

in

shown

chemically ion

a-Pt,Si

scanning

surfaces

with

of

formed the

(TED)

layer

terms

oriented

thickness

thicknesses

silicon

platinum

platinum

to

of

studied

the

spectroscopy

Pt

on

phases

was

film

were

diffraction depth

layer layer

n-type

reactions

the

for

three

or

in

at

used

Ph_ANio.gSi

to

growth

state

nitrogen

[1325].

for

a

glassy

two

silicon

clean

PtSi

in

for

unstable

to

with

of

phase

effect

was

depositing

growth

and

platinum

due

conjunction

PtrSi

AES

amorphous

measurements

patterns

formed in

phase

TED

showed

for

Solid

electron

and An

of

noted

with

a

understood

on

and

silicon

transmission

information.

Pt+Si

[1326]. on

be

in

were

uniform

substrate

separation

minutes

as

a

bonding

only

platinum

identification.

bonding

the

diffusion

using

could

deposited

of

isotope

20

STEM/EDS

did

silicon

sputter

consistent

deposited"

studied

the

films

The

was

grain-boundary

of

Thin

diffraction.

mechanism

into

was

for

developed

temperatures

preferential

deeper film

silicide

high

the

annealing

cross-sectional

ternary

growth

with

to diffuse

and

and

at

silicide

diffusion,

nickel

silicon

sharp

PtSi

techniques.

a

the

within

examined

which

Inside

a

have domain

thin using It three the

213 crystalline region that a

perfection

was of

other

abrupt

similar

lattice

250-350

lC, At

of

PtSi 600

perpendicular

the the

The

high

silicon

or

function RBS ,

forward

current

was

(700-1000

'C)

to

PtzSi

increasing

treatments,

causing

larger

undulation

layer

other

extended

workers

.

formed.

On

Pt2Si

silicide

than

to

descibed

annealing

at

persisted

to

with

its

structure

c-axis

showed

reflecting

the

a

three

[1334]. formed

by

metal

properties

a

and

interrediate

large

relationship

The

Film

of

silicide of

considerable

and

n-Si

silicon

degredation

by

high of

as

a

technique, measuring

Schottky

on

with

examined

measuring

techniques,

amounts

reaction

were

resistance

SEM

characteristics

dissolve

the

symmetry

using TEM

was

epitaxial

was

PtSi

studied.

interface

silicon

orientations

analyses,

volatge

found

on

epitaxial

of

no

paper

three-fold

temperature

X-ray

the

surface.

stability was

annealing and

~100~

boundary

Despite

related

an

epitaxial

cosputtering

that

a

little

with

temperature

of

Auger

PtSi

strained

PtSi/Si

platinum a

doaain

the

showed

showed

silicon

the

interfaces.

In

with

PtSi

pattern

but

equivalent

image

[1333].

together

multidiffraction

at of

"as-deposited"

'C to

and

silicide/Si

interface

400

high

undulation

epitaxial

studies

'C.

The

observed.

cross-sectional

the

was

diodes.

temperature

its

properties

[1335]. Thin

platinum

irradiated

in

frontside single

air

disordered

measuring

x

mean

value

given

M5ssbauer

The of

in

Crystal possessed

was

the

ionic

data

for

but to

of



laser

for

backside

furnace

glassy

wafers 1 ms.

White

irradiation

gave

annealing

PdSiCu

were

(13361

and

many

other

[1337]. of

LIII to

be

model

ytterbium

edge

X-ray

absorption

a homogeneously close [1338].

TmPdaSil

in YbPd.Si,

to

These

and

YbPdZSiz

was

used

mlxed

the

high

results

were and

determined

valence

valence

system

tenperature were

band with

limiting

consistent

with

[1339].

compounde

glass

iron

the

LCAO

[1340].

were

of

hexagonal as

method Hyperfine

studied

structures

arorphisation

systems

temperature ICP

silicon

Nd-glass

similar

states

shown

room

orthogonalised

Pd+iZrsJ

Pd,Sn

studied

on

a

coefficients

valence

at

effect

Other

X.11.5

were

This

by

multiphase

susceptibility,

valence

from

in a sequence

surface

photoemission. a

gave

deposited

pulse

expansion

solids and

sputter

one

silicides

thermal

Bulk

by

irradiation

phase

The

by

layers

a

as

PtsAm

result

of

type

study

interactions

functions

and

CusCa

to

Pt&m

of thin

structure,

self-irradiation

the

and

Ml)ssbauer

temperature layers but

were PtsCn

at

electronic

room

and

structure

paraaeters

pressure

investigated. underwent

PtsAm

rapid

temperature

of

113411.

X-ray

[1342].

214 Values

or

a wide

range

Ca,Pt,,

provided

for

the

compounds

SrPt,,

SrPt,,

species

= Lu.

and

structure.

more

were

were

AlPd,

the

anomalous

prepared

the

radius

electron

important it

(Ln = Sm,

Gibbs

free

energy

AhB,,, including

AlsPtz,

from

[1344].

or a-U)

Tb,

by

of

LiPt,.

Al3Pt5,

Dy.

formation

BePtts,

ScPtS,

were

by arc

BaPt,

for

favouring

obtained

heavy

fermion

Tm.

of

RgPt,.

and

with

M = Pd

melting

TbPtAl

favourable

factor

superconductors

Et- or

techniques.

results

between

Ha,

elements

X-ray

ratios

The

Y,

their

concentration

intermediate (&Fe

Gd.

characterised

Whilst

phase,

placed

LnMAl

M = Pt)

hearth,

Laves

been

interaetallic

many

113431.

The

was

have

of

SrPt,,

others

Ln

limits

the the

on

had

or

a copper

the

TiNiSi

formation TiNiSi

or

Prog.

Chem..

of

UP&)

&PtC, and

less

[1345].

REFERENCES 1

J.G. fnorg.

2

A.Z.

Taylor

and

Chem.,

M.G.H. Wallbridge. (1982) 279. E.R. Milaeva, A.I.

5 6 7 8 9

Sect.

A:

Rubezhov.

Prokof'ev

v

Sintete I 23-26 De&.,

and

O.V.

Okhfobystin.

Katalire. Materiafy 1980, Chcmogolovka

Plenar.

26 101 (1984) 32226~1. A.V. Roshchin. V.G. Veselov and A.I. Panova. J. Hyg.. EpidcmioT.. Microbial.. Immunol., 28 (1984) 17 [Chem. Abstr.. 100 (1984) 214724~1. and A.S. Dudin, Tr. Inst.-Mask. E.G. Rakov, A.V. Dzhalavyan Rhim .-Tekhnol. Inst. fm D.I. Mendeleeva, 125 (1982) 82 [Chcm. Abstr., 100 (1984) 166924nl. K.O. Christe. W.W. Wilson and R.D. Wilson. Inorg. Chem., 23 (1984) 2058. M.P. Neary and T.A. Wilson. Pr_ lkrrade FR 2.5J!6,593 (1983) [C&m. Abstr., 100 (1984) 105834ml. S.A.K. Lodhi and A.R. Khan, Pa&. J- Sci. Ind. Res., 26 (1983) 281 [C&m. Abstr., 100 (1984) 121691tl. G.L. Gutsev and A.I. Bolydrev. Chcm. Phys. Lstt.. 108 (1984) 255. Radiochemistry. 26 (1984) V.P. Domanov, B. Eichler and I. Zvara, Soviet [Chcm.

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3

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Tetrahedron M. Kurada

1119 1120 1121 1122 1123 1124 1125 1126

1127 1128 1129

1130 1131 1132 1133 1134 1135 1136 1137 1138 1139 1140 1141 1142

1145 1146 1147

1148

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1184 1165 1166 1187 1168 1169

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(1984) 157. V.V. Safonov

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Khir..

28

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2750.

254 1291 1292 1293 1294 1295 1296 1297 1298 1299 1300 1301

1302 1303 1304 1305 1306 1307 1308 1309 1310

1311

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1312 I.D. Romanova. N.K. Maksiaova, L.Yu. Potakhova, M.P. Yakubenya and V.P. Yanovskii, Poverkhnost, (1984) 106 [Clrer. Abstr-. 100 (1984) 112949f]. 1313

W.F. Kosonocky and (Infrared Detect.), 217990r].

1314

W.A. Tifler,

SPIE-Int. H. Elabd. Proc (1983, Pub. 1984) 167

Gov. Rep.

Announce-

100 (1984) 112453q]. Levy, A. Grob, J-J. Grob and

Index

Sot. [Chem.

(U.S.),

Opt. Rng.. 443 Abstr., 100 (1984)

84 (1984) 429

[Chem-

Abstr..

1315

D.

141. 1316 B.S. Lim and J.P. Stark, Mctall. 1317 A. Oustry, J. Berty, M. Cauront

J.P.

Ponpon.

Appl.

Phys.

A,

A35

(1984)

Trans. A, 14A (1983) 2557. and M.J. David. J- Wicrosc. Spectrosc-

9 (1984) 45. I. Abbati. C. Carbone. G. Ciucci. B. De Michelis, A. Fasana and R. Mondinf. Solid State CBun.. 48 (1983) 735. Sci-. 142 (1984) 1319 R.S. Markiewicz. C.J. Rollins and J.S. Brooks, Surf. Electron.,

1318

56. 1320 J.H. Weaver,

Cov. Rep. Announce. Index (U-S.). 84 (1984) 444 101 (1984) 306OOs]. Res. SympProc.. 25 (Thin E.C. Zingu and J.W. Mayer, Mater. Interface 2) (1984) 45 [Chem. Abstr., 101 (1984) 117098hJ. V.M. Bermudez. Appl. Surf. Sci.. 17 (1983) 12 [Chem. Abstr.. 219337t1.

[Chem.

Abstr.,

1321 1322

Films 99

(1963)

255

##et_ semicond., Proc. Int. Symp., 5th. (1983) 473 A. Cros. Passivity [Cher. Abstr., 100 (1984) 148733~1. 6. Queirolo and G. Celotti. J. Appl. 1324 S. Mantovani. F. Nava. C. Nobili. Phys., 55 (1984) 899. Ellwanger and Y. Tamuinga. Proc. 1325 A.E. Morgan, W.T. Stacey, R-C. SPIE-Int. SOC, Opt. Eng.. 463 (Adv. Semicond. Process. Charact. Electron Opt. Mater.), (1984) 33 [Chem. Abstr., 101 (1984) 48944j]. 1326 El S.M. Aly and J.P. Stark, Acta Hetall.. 32 (1984) 907. 1327 El-S. M-1. Aly. PhD Thesis. Univ. Texas, Austin, 1983, Diss. Abstr-

1323

Int. B. 45 (1984) 981. 1328 L-R. Zheng, L.S. Hung and J.W. 1329 1330 1331

1332 1333

1334 1335 1336 1337 1338

1339 1340 1341 1342

1343 1344 1345

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