Copper, silver and gold

.. IJJPPER;

SILVER

: ANNUAL

AND

GOLD

-. : SURVEY

COVERING

E. SI~GLETdN

and A.

THE

YEAR

1974

TUINMAN

NationaZ. ChenticaZ Research Laboratory, Comcil Industrial Research, P.O. i3ox 395, Pretoria

for Scientific and

0001

(RepubZic

of Sot&z

Africa)

contents ^^_^^1A^

Organocopper

I.

Reaction

Ii.

of organocuprates

1.

Organocuprates

2.

General

IV.

Catalysis

V.

Complexes

and

related

lithium-copper

reagents

414

compounds

414 423

reactions

430

bonds

by

Gold-carbon

VI.

and

catalytic

Silver-carbon

III.

407

compounds

saits

silver

433 442

bonds of

general

446

interest

452

References

'NOTE:

This their

article

on organometallic

reactions,

is only

derivatives

comprehensive

of Cu,Ag and Au and

if read

in conjunction

with

the survey for 197.6appearing in this journal.entitled "Transition Metals in Organic Synthesis", by L.Hegedus. Duplications in these two surveys

have been minimised.it.Urg&nome~a~.Ghem. .I.

Crganocopper 11__1_______

,ijjj~i4./5)‘,~L-‘~‘ilr.J

compounds _....___1..1

A series of copper alkyls RCuL (R=Ne,Et,Pr;L=Bipy, tricyclohexyl

.408

1.

: :

.. :

,_:

.-, I. .. : -.

'.).:

~_~,-~-l~~~~.:_-~ 1;. "-'-id -fc': :,:.._. .- ,'.:-;--:

;. *. phosphine) and PpeCu k&v& been prepared frdm C&ica6)2 ~+:R;A~(oE~)'. .. -':-._: _: -. _ ..... :.:_ -.-. .- .. ~. .,t . ..-. .. in the presence or.absen& of L in ether at lo& temperkires. -Only the _- _I::-.

:

CO,
..

:_-:

complexes are thermally stable and‘fnrther react-with'

RC~(P(C~H,~,)3)

to give

and

Mek0,Cufk(C6Hil)3)

:ieC02Cu(c02)(P(C6R11)3)

i L : ...

_ii].

‘%I.

Two new stable organocopper derivatives from aryl-Cu compounds and or malonitrile~are

.bis(diphenylphosphinosulphide)methane

Copper(I) t-butoxide with NCCH$02d heated in DMF, decarboxylated decarboxylation product

13 j-.

in THF

to NCCH2Cu.

gave

..~

reported 121.

NCCk~C~-$i;~which, when

With (NCCH2C02)2Cu the

is accompanied by reduction to the same

cytinomethylc&pk(I)

A preliminary X-ray structural determination of [Me2P(CH2)2Cu]r

has shown its dimeric nature (x=2).

El

Cu-C bonds averaged -1.96 i 143.

Me,P

@ PMe;

PMe, \

>

Me-,P

/

-M-CH

2”

\

(M

(11

=

PMe3 Cu,Ag)

(2)

Other copper and silver ylides reported were [(Me3PCH2)2Cu]Cl and (2) from

CuCl(PPh3)

and

MC1

(I-f=Cu,Ag) with

INMP

Similar

respectively.

mixed

ylide systems were .characterisedwith the.ligands PhMe2PCH2 and MePh2PCH2*

together

with

the

product Me3SiCH2CuCH2PPfe2[5]-

route to vinylktaIZic-copper(I) and RSi(CH=CH2)3(CuCI)2(R=He,Ph)

An alternate.synthetic

complexes R2Si(CH=CH2)2(CuC1)2 from CuCl or COD&Cl

(R=Me,Bu,Ph)

has been found-161.

The IR spectrum of the interaction of CO vith a series of matrix isolated fluorides including CuF2

has been recorded.

correlated

'band was. ~’

The CO high .fre&ency

..

.to the strength of. the electric; field.of thr metal

ioirgt

the

‘. : ,.

..

:_

..:

:.

>.-

:..

-

..

...

409

‘.

.-,;.~. -. ._''&~kinet&s yc &A&~j-~~]; to -give dimethylcarbonate &turelof

:

of-carbonyiation

of [Cu(OMe)X] (X=C1,Br,MeC02)

-have been investigated.

.The-autocatalytic

the reaction.tias.&scribed to cuprous carbonyi formation.

The rate

deter&&g step appears to be the rearrangement of a mixed valence dimer . like [Cu(OMe)X.Cu(CO)X] to a labile carbomethoxycupric species [S]. The new heat-stable copper carbonyl and isocyanide complexes t-Bui)CuL(L=CO, CNBu-g) have been prepared, with their thermal stability being attributed to the strong o-characteristics

of the 4BuO

were also studied (scheme 1) 191.

co PhH

90"

-

Insertion reactions

A review on the advances in the chemistry

of isocyanide complexes has appeared [lo].

(t-BuO)aCu

ligand.

13C chemical shifts, lJ(14N-13C)

ct-6uO)Cu

+

t-BuOCOBu-t II ij 60%

(1) t-BuOCuCNBu-t

.-q-p

(2) Me1

Me / H

C&ZdNBu-t

10 fold excess

=\\

N&I-t

t-BuN=CHC5H4CuCNBu-t t-BuNC

(Scheme

1)

coupling constants and stretching frequencies of the isocyano group in the isocyaxiides [(Me3CNC)4CulBl?4 and [([email protected])4Cu]C104

have been determined.

The results were discussed in terms of inductive and mesomeric substituent effects on the polarisation and charge density of the -C-N-C bonds[ll].

4i0-_

The

.:

_

l3 C

.. . :

,y..

NW2 spec&a.of.cycl&olefincbpper(i) complex& -have tieen: .~~ _: .. .The change in the che&aI shift of the vinyl.carb?n upbn

examined.

co-ordination was compared to the change observed in the proton spectrum, and the Dewar-Chatt-Duncanson

model for olefin-metal-bondi&was

used.to

compare chemical shift.changes observed in polyolefin and mon&oIefin ComThe roie played by r-back donation i&the

plexes.

relatively.large

upfield

The use of copper(I)

shifts observed in monoolefin complexes was described.

triflate as a 13C NMR shift reagent for olefins was suggested

1t.is

1121.

of interest to note that in recent correspondence the validity of many papers rationalising

13

C chemical shifts for carbon atoms bound to transition Specifically,

metals has been convincingly questioned.

very small upfield shifts for olefins'bound

to d

10

the proposal that .

Ag(1) supports the linear

relationship observed between the shifts of a-bonded carbons and those of a-bonded

carbons in the same molecule 5s hardly

convincing

as ethylene

bound

to dl" Pt(0) exhibits a marked upfield shift on complexing as do olefins bound to Cu(1) 1131.

Calculations on, [14] and the properties of

1153, metal-olefir. n-complexes of ethylene 1151 with Cu,Fe,Ni,Ag,Cu+,Ni+ on the propylene-n-complexes in the

complexes

Copper(I)

ions

depends

and Pd+ have appeared.

The calculations

‘revealed that activation of the C-H bonds

greatly

in Y-zeolite

1143, ally1[14] and propylene

on

the

nature

of

the metal

ions

absorb ethylene-in a 1:l ratio.

[IS]_

Characteristic

IR specroscopy bands at 1428, 1533 and 1920 cm-l-are reported ;icj.

~CUGC:;ICI.

HgC12]n and [(CODCuBr)2HgBr2]n have been prepared from [CODCuX], and HgX2
A preliminary X-ray structural determination of the

compound CU~(CF~CO~)~(C~H~)~ of 4 Cdsin

(3) has appeared.

a plane with.trlfluoroacetate

Each copper has.a co-otdination of three the

meta-position.

iCu(CF3C02) (olefin)y]x

Other

cl&fins

(olefin

readily

= indene,

The basic framework consists

groups bridging two copper atoms. by forming n-bonds replace

the

to benzene

benzene

y = 1, x = 4;olefin

group

in to give

= cycloh-a-+,4-

.‘.

411

diene, cyclohexa-1,3-diene,

y = 4, x=4), and it was postulated that Cu4


[X3].

Eleven complexes of benzene and hexafluoro-

benzene with Ti, V, Cr, Mn,'Fe, Co, Ni and Cu have been prepared and their thermal stabilities determined[lg].

The spatial arrangement of the

Cu03SCF3 matrix has dictated a unique stability ordering of alkylaromatics based more on their-shape than on their sr-basicity. This property was used as a basis of the separation of p-xylene from other CS arenes.

The mechanism

of the ligand exchange reaction was discussed and equilibrium constants were determined

[20].

Increased carbanionic reactivity of the alkynyl group in copper or silver organo complexes by strong

o-donor ligands e.g. Bu>

facilitates CO2 insertion into.the M-C bond (Scheme 2) [Zl].

or t-BuNC, Relevant

parameters obtained from the crystal structure of [iCpFe(CO)2(ECPh))CuCl]2 are Cu-Cl 2.29&

References

p_ 452

Cu--Cu 3.07; and Cu-C (ethynyl) 2.012

The acetylene is

(4)

412..

..

..-

: PhC-PH

t

t-BuOM

.. .. ye-: .RI-.

:: .. "

B&P; -

PhC&CM

80’_

,_.-, ~... _. . _. -_ --..

THF.

;‘I

(1) co,

‘.

..

PhC=CCO&le &JF~Jg.,~):-_

(2)&i.. M=

.:..

:

-. .. ‘.

-;

Cu,Ag

\ CC&Me (Scheme

2)

s-bbnded to the copper and the CuC2 moiety is coplanar [22]. on the structure [23] and preparation appeared.

2.74;.

Full papers

[24] of Cu41r2(PPh3)2(CXPh)8

Refined mean interatomic distances are Ir-Cu 2.87;. Cu-Cu

(5) have --

Each Ir atom is bonded apically to a PPh3 ligand, with Ir-Pa2.26;.

.. .. -.. ‘.

_

-.

...

413 The

4 phahylethynyl

ligands are o-bonded

Each aketylenic fragment simultaneously interaction and

Cu--C

1231.

with

6

L&and

Cu atoms

is 2.185;;.

in the

Each

Cu

to each Ir atom with Ir-C=2:04;. participates

octahedral

such

that

Cu--C,

?ris

1.99.;

is thus bonded to 2 acetylene moieties

substitution of Ar4Cu6X2(X=C1.1)

which formed ArR exclusively on thermolysis. .R=PhEC,

meridian

in an asymmetric

with RLi produced Ar4R2Cug The ArR (Ar=W1e2NCsH4;

ES-!$eC6HqC5C,2.4,6-Me3C6H2C5C) is presumably formed by an intra-

molecular process bond formation.

via

a

concerted

homolytic

Cu-C

bond

The specificity of the thermolysis

breaking

and

C-C

was explained in terms

of a template effect as seen in (6) [ZS].. Linear dicoordinate Cu(1)

@C

Referencesp.452

@

C(brldge)

0

=u

414

:

., ..-

. . :

&6e&ikbs&ed

in rhe-par~i8lly.refined

st~X&&k.'~bf

.’ ._: ,’

Cp&(PPh3)2::

.- _. -(C%CPh)CuCl [263:

Far.IR and.absorptioq

spe&ra:of

a series of.monomeri& ._

-

.. and-polymeric copper-or~~noacgtylides spectra-of- tSe polymers

having

have been.measur&dL

The absorption

.-

Cu&CR(R=Bu,CH2=CH,Ph.PhC%,

the ;m_units

p-PhCeCC6Hi) and CuC%QCGCCu(Q=p-phenylene_4.4:-biphenylene phenylene) reflected charge transfer'between

and oxydi-p-

Cu d'electrons and ligand-x-

electrons [27,283

A review on cyanide complexes of the transition those of Cu,Ag and Au has appeared'[29]. copper cyanide compounds, (BPII~)~

(7)

and

metals including

The crystal structures of the two

[Cu~<2,2',2"-triaminntriethylamine)2(CN)2]

~-cyano-bis<5,7,7,12,14~14-hexamethyl-1,4,8,11perchlorate

tetraazacyelotetradeca-4,11-diene)dicopper(II)

(8) have

been reported.(7) contains trigonal bipyramidal copper with the amine occupying 4 sites and an axially C-bonded cyanide ligand (Cu-C l-87% in the fifth position.

The cation is dimeric because of hydrogen bonding

of the cyanide nitrogen to hydrogen on the amine f3ii].In (8) the ligand bridges two copper atoms [31].

Stable mixed

cyanide

ligand copper cyanide

.complexes of formula [Cu(Phen)2CN]X.nf120 (X=C1,Br,I,N03,C104), Cu(Phen)2 (CN)2 and Cu(Phen)(CN); have been isolated from aqueous solutions [32]. A study of the kinetic reaction of CUDS-

in Fater and aqueous methanol

by stopped flow-techniques has found the reaction to be Second order in Cu(I1) and inversely fo a reaction

II.

2.

between

to the uncomplexed

proportional Cu
and

CN'-.

CII(CN),.+~- occuring

This

was

attributed

1331.

Reactiors of organocuprates and related reagents _^^^^^_^^ ^_ A__^yA^^_A^^ _A^ A_lA1_ _lA^_^l.. Organocuprates and Zithiwn-copper conpowzds ESR studies showed that CU(RNC)~ and Cu20(RNC)m complexes transfer

electrons to various v-substrates such as nitrobenzenes, benzoquinone aud

-..

‘_

...

j-

-.

415

.’

tetracy&oethy+ene,

thus producing the anion radicals of these species [34].

The complex metal hydride LiCuHg was prepared by reaction of LiPleZCu with LiqlH4

in ether.

b&low 70° [35j.

Referencesp.452

The yellow precipitate was shown to be I

reasonably stable

_ -416

.--. :::

PhC=CC02R

_:

. _

p

LiMeaCu

-so0 (9)

Ph\

,A-Li

,[c=c\co~R

,,/‘==\

-+I

LiMezCu

PhL

-

.,”

.'2

=GP

:

Phw

+

l=hu

PhSeBr SePh

88%

_

83 % (Scheme

31

The formation of a covalent Cu-C bond iri the conjugate methylation of the phenyl acetylenic ester (9) is reported. protonatiori w&e

performed at -80" only the_- c&-isomer

proving c&-addition reaction mikure

If the reaction and subsequent

of keagent.across

the triple bbnd;

On Wa*g

,. .:..

to_ RT before pr6tonat~on_th&~int&m~diate~:'(lO).&d

-.

l

reached equilibrium axid 80%. of the &zns-isom&(~3)

:res<ed.

:. _:

--

: ;

‘_ .;

:

.

-. :

the

.. :

.. .-

(12).

Similarly ...

_ .-.

-_. -. :

:

.ill) was-fq-ed,

.I

.-. ‘. : _.

417 ietentioh-of

configuration

Rege&ration

of

by

trapping

(scheme

the

3)[373.

was

the euone ekolate One

established

moiety

after

with

PhSeX

and

oxidising

with

the

steps

used

in the

selective

of

hfMezc_1?

1383..

Et(Me)C=CHC02Me

enolate

(18)

regeneration

of the

enolate

as

uses

Stereospecific

phenylisoquinolinone

intermediate

(16)

reaction

alkylation

triphe&lphosphorone

the morphine

the

conjugate

3-methyl-2-pentenylidene

gave

for

the

silyl

ether

with

LiNH2

and

(19).

partial

alkylation

gave

(17)

OC(Me),OMe

. . .

OH

racemic

Referen~p.452

..

-_.

peroxide

e.g.

of EtCGCC02Me

of LiPh2Cu

[39].

[36].

achieved

synthesis

LiMe2Cu

(17)

was

hydrogen

addition

fragment

(14+15)

Trapping

to

(16) of

purification, (20)

in

47%

the

‘.

418 overail.

yiela

lithium

dialkyl

[40];

.. organocopper

&rat&

,& enon&

treated withyu-silylated

._

enol2tes,

under&&

-1: :

generated

by the action'of -; _.. ~, _: regio&ele&ive.annelatiqn:wh~en

vinyl ketones (22) -f (23) f41.j.-The Presence of.

dapper ions wss found not to be necessary for the regioaelectivity of : the subsequent alkylation steps-

Rven enolates could, under aprot.ic

conditions,be alkylated regiospecifically, regardless of whether they were generated by LiMe Cu action on enones (21)+(22)+(23), or hy methyl2 lithium reaction with the vinylsilyl ether @4)-+(25)+<23)

LiMeaCu

1421.

The enone

_

/O /x

SiMeg

(23)

(22)

OSiMe, LiMe *

(26) was prepared in 6 steps from the epoxy lactone (27) by a route involving ring opening of the epoxy lactol methyl ether (28) with the vinyl Gilman reagent, Li(CH2=CH)2C4

to give (29) 1431..

The epoxidea .(30)

(R=R'=Me,Ph;R=Me,R'.=Ph) were cleaved.by LiMe2Cu-LiI or MeCu-LiI to give a nixture of ~~‘c=mcN,

RR'C(OH)CH2CN,RR'C(OH)CNMeCN

and. CR'RC(0H)12C~~N.

The relative yields of RR'C(OH)CHMeCN and [RR'C(OH)12CHCN were increased by using a 1:2 ratio of (30) and the copper-containing dimethoxyphenyllithium

reagent 1441.

The 2,6-

cuprate reagent gave 2,S-(Me0),C6H3CH2CH(0H)Me

:_

._

419

(261

R = p -PhGH,NHCO

.(29)

R =

with

propylene

R’=

The

latter

The

final

; R’ =

Co(Cy)4

Me

H

and

oxide,

reac.tion; step

no

reaction

in the

synthesis

of

R =

R’=

R =

OMe;R'=

with

p reduced

in fact,

(27) (28)

(30)

0

H

trana-2,3-epoxy-6-methyl

heptane.

2,6,2'6'-tetrameth~~ybiphenyl

1451.

tetrahydrojasmone

(31) was

a conjugate

(31)

addition (33),

a copper

a fragrent

(32) with using

using

catalysed

component

LiR2Cu.

The

Grignard

of vetiver

undesired

the heterocuprate

oil,

epimer

was

of

(34) was

(35) [47].

isophorones

with

[46]_

largely

The

(36) with The the

isophorone reaction

mixture

outlined

(38) 5

in scheme

References p. 452

Ni(acac)

and

LiAlFle4,

2, producing

2-cyclohexenone

of dibromostilbene +

(39). 4 for

Evidence the

85%

reaction

suppressed

reaction

of by

is proposed

Cu(acac)2

was

found

to be

With PiMe3. Cu(acad2

of the

1,4-addition

product

[48].

(37) with supported

formation

by

B-vetivone

In a study of transition metal

a very much less.efficient catalyst than Ni(acac)2. was more efficient than

Racemic

synthesised

Li[EfeCuBr].(BuX2XH)2.

to proceed via the intermediate

catalysed reactions

reagent

of

the

excess

LiMe2Cu

the reaction dimer

(39)

produced

mechanism [49].

Treatment

of

(ratio

(32)

5: 1)

(34)

\

-.

.’

.‘CUQ

-

Lie

:

(36)

l-pyrrolidino-6-chlorocyclohexene

with

LiR2Cu

was

with

Li(containing

reacted

sequentially :

at -780

to give

-3S".iu

the

E--and

were

obtained

ratio.

from

by

Yere of

complete

formed The

[Sl]:

and

reactions

alkylated

which

(Ke2N>3P0

CH2=CHCH2Br

Corresponding

Iodovinyls ._-

of

4% Z-isomer)

is accompanied

presence

[(E)-MeCH=CH]2CuLi,

presence

(96%

in ether

allylic by

copper

of

and

(43)

establish the-ally1

or lithium [53]:

CuI

at

yield

in 90%

y-(42)~allylated

(Z)-CHD=CHCH2Br

configur&ion

at 13"

of Me(CH2)71

dienolate

transposition

(E)-MeCH=CHCl

[SO].

1% Na)

MeCH=CH(CH2)7Me

organomagnesium

CuI.with'retention-of

(40)

on addition

(r-(41) and

the

with

gave

products

in a 44:56 that

y-at&k

group

[52].

compounds

in

..

the

..CH2=CRCH2Cl.(R=H,Me)

‘;

.. ..

: ._

-_

-.-. ..:_; .‘Br

._-.Ph

:.

421

._

,PbMe LiMeaCu

w

+.

P

._

.: \

\ l3r

Me

(37)

LiMqCu

(38)

Ph

Me

(Slob%‘) I

Br

E3r

Me

LiMe&u

‘;\_/ ?,,

_

pT_--__/

(fast)

L-

\Cu \’ (Scheme

underwent presence

[541with

DMF

exchange

of CugClg A complete

CuCN

evidence of

halogen

iodide a.&.

has

ArI

ReferenwR.452

with

to give

the

replacement

been

indicated by

Ph

Me

\

effected the

chloride + CuCl

aq- RX(X=Br.I)

of

iodide

groups

by

CN in

in hexamethylphosphoric

an aryl

[ArCuClI]

+

of an arylcopper iodide ArCl

at 44-80° in the

CH2=CRCH2X in 72-W%

corresponding

intermediacy when

+

excess

4)

was

+ CuI

treated [56].

(44)

triamide in

the

with

and

yield (45)

[55].

Kinetic

substitution CuCl

in refluxing

Me (44)

Heterogeneous have

given

of ethers position whereas

reactions

copper(T)

alkoxides.

by displacement of primary

with

moderate

yields

isonitrile

which

of halide

from

were

[SS].

or phenols

useful

organic

generates

a copper

of cyanides 5)

are

alkoxycopper(1)

involving

(scheme

alcohols

alkoxycopper(1)

secondary

or a mechanism

between

obtained

Isopropyl

either

actions

sulphide.

added

producing

products

:

of see-butyllith&m

ally1 of

type

(46)

decomradicals,

1571.

Only

with

generated

process

trityl

by

the

Ph.&M + -

RCSN

5)

and

bromides-exclusively the

formation-

radical

reactions

I successive

alkoxy

a free

thioallylcopper,

(Scheme

the

Thermal

to operate

L%Cu

methylcopper

for

intermediate

appears from

reagents halides.

reagents

hydride

and

(scheme

cuprous at 6)

the

iodide carbon

[59].

on ally1 atom

isopropyl

y to sulphur,

R-CR=CR'CH=CRX(R=H,

.:. M&&:R'~~H,Me; .reaction

423

.(

X=PhS,Ph)

of OAc.and

were

PhS

2

.. (R =Me;Bu) in ether

prepared

groups)

by

at 0 to -35O

production

of a,&epoxy-ketones

(47) using

two

equivalents

in 23-80%

treating

for

of LiMe2Cu

[603

a x,2-elimination

complete

with

LiRzCu

Non-alkylative

corresponding was

(via

RCH=CB'CH(OAc)CHXSPh

1 - 1.5h.

to the

yield

#3-hydroxy-ketones within

5 min

at

0".

(47)

The

cuprate

out

in the

has

been

is a better presence

extended

substituents substrates and

the

brought ture

2.

reagent

of unprotected to include

adjacent (scheme

from

by

-78"

Genera2

the

7)

1621.

reductive

to -loo0

and

the the

reaction reagent

reaction

groups

1611.

elimination

This

in both

for

the

carried

reaction - and

overall

dropping

halo-

polyfunctional yield

8 was

in scheme

and

PBu3

be

of acetoxy

represented with

can

to be viable

increase

the

tempera-

[63].

on Au

transition

yield

by

treating~Me2C=CHCH2CH2C(SPh)=CHC02Et

CuC12

was

dimers

as a cocatalyst from

c&-

in alkylpolyamine

nitroalkanes rhe heterolytic

Referencesp.452

[64].

n-bond

and

used

complexes

metal-carbon

to Cu,Ag

salts

the

catalytic reactions

A review

chloride

as

proved

A dramatic

of

complexing

Li/NH3

carbonyl

to carbonyls,

stereoselectivity about

than

to oximes splitting

Ethyl

in the

and

geranate

was with

preparation

tmxs-geranylacetone

solvents in good of

fission

catalyyse yield.

H 2,

is

An

the

postulated

synthesised M&&I

and

references in 99%

CuI

[65].

of allylpalladium [66].

homogeneous

initial

contains

hydride,

as an

Group

IB metal

hydrogenation formed

intermediate

from [67]_

of

_

z g

0

l-i

H 2cX

82 %

or 2p

(Scheme7)

OAc

0

C1CHMeCH=CH2 7~1s isomerised to MeCH=CHCH2C1

in dioxane at 25" with;(i)

CU(OAC)~ within 150h or (ii) Cu(atiacT2 or CuC12 within 1OOli 1683. PdC12-CuC12 in acetic acid catalysed the rearrangement of the.endo_ and'

425

exe-isomers

of'5,6-(a-phenylene)For

xiaphthylene)norborn-2-ene. proposed

and

depress added

the

addition

carbonium

ion

to reaction

of Hg-C

bonds,

form

Hg,

e.g.

AcR

and

Me2CHBr,

A study

of

condensation

mechanism dioxide

the were

intermediate

by oxidative

decarboxylation

Pb(OAc)4

Cu

and

RCECC02H

c741.

in nitrile

complexes

Referencesp.452

solution

of Cu(II)

steroidal

containing

organocopper

has

9)

with

large

concluded

and

by

Cu

that

2+

ions

of 4-5

presumed The

labile

(Scheme

9)

of

of AcO(CH2),CHRtC02H not

affected

(R=H,C02H)

was

decarboxylated

to

1711.

equivalents via the

by varying up

type

Sulphonyl-1,3-dianions of

CuC12.

a thiirane-S-Sproducts

formed

(n=2,3),initiated

in

gave

CH2=CHCH2Br

[72].

mol.

ratio

amounts

a Claison-Schmidt

to proceed

[73].

in

LCuHCL=(Me2N)3Pl

complex

by

the

copper

ligands

to 80%

yields

by

CuCl

1751.

condensations

of diphenylmethanimine

have. been

reviewed

(=L) with

copper

to

halides,

and.CH2=CHCH2PO(OCHe2)2

addition

but

react

is

tended

ketones

Compounds

[70].

was

The Ullmann ether of the

amounts and

(II)salts,

solvents

reaction

formed

the

(Scheme

the

intermediate

With

catalysed

elucidated

alkene-Cu

acetals.

CH2=CHCH2CH2CH0

by

an

of 5,6-(1,8-

corresponding

The

not

to

Small

LCuCH2COR.

to olefins

was

salts

(R=H,alkyl),

is specifically

oxidised

latter,

1691.

aldol condensation

the

the

Hg(CH2COR)2

88%

unrearrangement

of cyclohexanones

produced

Cu2Br2,

were

formation

a-haloacetals

CuC12,

the

of-copper

mixtures

ethylene.glycol,

and

[76].

The

chlorides.

role i-e.

The

..I:.

426 &LCl,

.-: . :. .CuL2Q;CuC12G-and'CuCliL2;

-._ _._._. -- . .,. ~...

‘in:..rhe--cAidati& _.~

. _

.... _. -. -.:-__.;.

cotipling~~&rL

1 ..; studied.

ha&

:.-

: .......

The effective int~ekmediate-was found to be CuClL andthe

effect: ..

of oxygen.on the reaction'was'.noted [77].'.-When MeI,vas ‘used-as a' radical

__

:'

L

trap in the reaction of-p-NO C H N '?BP- with [Cu(MeCN)A]C104, p-IC6H4N02 2642-h was formed as well-as No2wN02

and N02e

N=NBNO2.

From a . study of this reaction the mechanism W&S postulated to occur via aryl radical addition to

Cu(I) followed by reaction of the.resuItant

intermediate with another aryl radical to produce diarylcu

arylCu(11)

This can now form biaryls in a reductive elidination step

(III) species.

or be reduced by Cu(I)

to diarylCu(II),

reduced to organocopper(I) ions to produce azoarene

which in turn, can be irreversibly

compounds capable of combining with diazonium

[78].

Benaothiazole was treated with p-IC6H4N02

in the presence of Cu20 producing

(48) in 72% yield.

(48) (R=MeO) and 2,2'-dibenzothiazole

1791.

Also prepared were

The reaction of p-Tos-CR

with R'MgBr in THF over LipCuC14 at -7S" gave good yields of EE'(R=e.g. Et,Ph,octyl cyclohexyl: R'=Et,CMe6. Ph,cyclohexyl) to RT [80].

on slowly warming

A simple and convenient method for the preparation

of vicinal alkoxythiocyano- and alkoxyiodoalkanes from the reactions of

R =

NO2

(48)

:

bee:+. y--

(49)

olefins with Cu(I1) in alcohols has appeared [Sl]. -The two-new products E,Z-PhCH=C(C02H)_~(COZXI)=CKPh and the i,b-compound were prepared in

..-.

.. 427

.92% yieId.by the oxidative. coupling of.-trans-PhCH=C
rotational isomerisation were

(Scheme

the highest yields [S3].

by scheme 10, as this method gave

10)

The reaction of CH,=CH(CH,),CHClCH,CC13

CuC12 in MeCN containing Et3N-HCl gave cis- and trons-(49) intermediates.

Other cyclisations were reported

[84].

via

and

radical

Isomerically pure

trans-1,4-dienes were obtained by a reaction sequence given in scheme 11[85].

R'CsXR2

*‘\_/**

CUCI

\**,R3 --

H/

'RX

“‘1 /**

H/c=c\c_/H / \ R2

H2C=CH-Cl$Br cut3 (Scheme

hexane

“\

/**

H/==C\CH 2-_CH=CH

11)

Ref&ne&p.452

.. :

2

428

-_-__;

_

,__

__.

‘;

.l’_.--l~(_..I:_‘.l-.~i:,:--

‘I

....:- :..,

The olig&ierisations

I cdmpoun+s &reviewed with~termiual

:_,r-,:; ;_-

-_z

7

in the ptieoen&of . . . . .tra&tion..&al-:.:. ... y :.

of acetylenes

:

[86].. Propargyl and allylhalides

alkynes inthe.presence

of &(I)

have been.'~onden&d~;

salts. -.The role of-.&? and .'

the influence of the leaving group are discussed--[&].

Un&mmetri&fly.

coupled products were obtained from reactions of RCu and R'ECCu;

--...

With

conjugated acetylenic acids and MeCu, similar products are obtained from .. 2+ species have been decarboxylation followed by coupling [88]._Cu(~~)5 shova,

by

EPR,

to occur

PhCZH

catalysed

by

HOCMe2CH=CHCZCH

in the

homogenous

Cu(py)4(N03)2.[89],

with

Cu2C12

and

in the

in ethanol

and

[go].

benzene

presence

(ii)

oxygen

of Cu2C12

trarzs-HOCMe

.2

oxidative

Oxidative

gave

yielded

condensations

using

CH=CHCeCCH2NEt2

with

as catalyst

Treatment

[91].

of

HCHO

The linear acetylenic polyamines,e.g.

Cu2C12

84%

and

acetylene and

(53)

from

the copper

arhoxaldehyde

The with

were

prepared salt

from

(52)

(X=X'=X"=Cl,Br;

were

(R'= <'

obtained

R=CN,CH=NOH)

trmzs-trans-

the

~PLVZS-

Et2HH

of m_IC

piperazine and H CSCH

64

with

min

to RCH2Cl

and

indanone up-to

(R=CH2=CH,

from and

and

the

) and (Me0)2CHCeCC~, 2 with 5-iodo-2-thiophene

halogenation

of HCECR

mixtures

CuC12-CuBr2

with

[95].

Mono-

CuX2(X=C1,Br,SCN)

several CH2=CMe,

hours

respectively

MeCCl=CH) using

1 ,, _.

CuCl

coupling

(X'=Cli

and

dihalogenatiqns

tooR.from

.;

-.

[96]:. Addition

of .: HX(X=Br.I)

_Cu2C12.a& catalyst-g&e

.~.I 1.

,~

~... ~. -. -, .i , _.. -.. .: ._.: :

of

-.

between

.30-50

in

Radical addition of XCClS (X=Cl,Br) to CH2=CHCN and

CuX2 gave high yields of C13CCH2CHXCN a-tetralone-and

trans-

[93].

X'CH=CX"R

X"= Br; R=CN) 1941.

of

(52) (R'=(OMe)2,R=(MeO)2CH)

of P-ethynylthiophene

respectively

products

CuX2.

The diacetal

of

(50),were prepared-

in aq. NH3 gave 39% of m-IC6H4CZCCu, which OR Stephens-Castro gave 5% of (51) [92].

of

(i) trwzs-HOCMe2CH=CHCeCCrCCMe20H

by a Mannich reaction of dimethyleth~ylcarbinolfonnal, HCHO,

couplings

dimerisation

in pyridine

Corresponding

HOCMe2CH=CHCeCC~CCH=CHCMe20H. acetylene

phase

: -.

T . . . . _ :.:. : ‘. -,

:

.:.

: -.

(52)

RCH2X

1971.

cyclohexene formation

knd

kinetics

halogenation -chlorinations

p_ 452

of

but-2-ene

of.dicblorides

chloroalkyl

Refer&es

The

(53)

in the and

intermediate [IO23

and

thermal

the

1981.

reactions

dark total A series

the

kinetics

of acetylenes

in the

have

of CuCl

been

2

and

studied.

styrene, The

nonstereaspecificity of papers

of oxidative presence

of

on the

indicated

a

oxidative

chlorinations (i) copper

exclusive

salts

and and

hydro-

430

:

phosphines

[103]

intermediate

(ii)

copper

ClCuCHyCHCl

[iO4~105~

mercuric'halides-

and

was.postulated

in-one

_.

case

ha&

a&-red.

The'

-. ..'RCCliX(RL

‘[iO4]..

.-.

Cl,X=Br; R=EIe0,C,Et02C,X=C1) underwent heterolytic addition to R'C%=CR*C; CR3(R'=R3=H,R2=H,Me;

R'=R2=(CH2)4,R3=H;R'=R2=H,R3~CMe20H,CMe20Me,CM~EtOR,

CM~BUOH.CM~~C~,CM~~OA~)

The

w(=O)10.2

new

copper

1 catalyses

in

ROH

complex

of

(R=Me,Et)

containing

the polyoxime

a Michael

type

[106].

Cu20

.

f(CH2)1.6[C(=NOH)C(=NOH)]o_3

addition

of acrolein

and

an

alcohol,

to give exclusively B-alkoxypropionaldehyde. The copper complex, after treatment with hydrazine hydrate, absorbs O2 and CO [99]. Copper salts catalyse the

reaction

isopropyl

of

thiophene

carbonates

ylides. [1011

with and

[loo],

(scheme

12).

diisopropyl the

It was

peroxydicarbonate,

cyclopropanation

suggested

that

the

forming

thienyl

of olefins

by

latter

be a more

may

sulphur

readily accessible route to cyclopropanes than diazomethane reactions[lOl].

Ph*L%*

Cu (acac)a

-!-

(Scheme

III

Silver-carbon _I_^^_ __^__I

-

PhaS

+

74

12)

bonds 1---1

The formation and thermal decomposition of several primary and secondary dLkylAgPBu3 complexes has been studied. For BuAgPBu3 the evidence points to a process in which C-C bond formation is concerted with Ag-C bond breaking. For

see-BuAgPBu3

Addition gave

the

of AgOAc

a yellow

in pyridine

orange

in t'acuo at 25"to

products

precipitate produce

point

to a possible

to an excess

of CR2N2

of Ag2CN2py.

a crimson

complex

Ag-H

intermediate

in ether-at

Pyridine

was

of formulation

-So

readily

[107]. rapidly lost

431

AQ \

i?

A!2

AQ

AQ

F -_Nc

(54)

AgCN

reacts

withKSCN

characterised gave

the

by X-ray

alkyl

of which

has

rhodium

atom

is essentially

Each

atom

is linked

parameters

observed

bond

distances

and

to farthest

series

often

may

Opposing

explain

substitution olefinic support

been

and

of

copper

[114].

(55).

lie

The

tetrahedral.

bonds.

Rain

l-19-L22;i.

The

of complexes

discussed on

the

K values in the in

between

and

crystal have

data.

mean

Ag-C 2.34

- 2.64z

for Ag(1) values

structures

for

This

influence

with

complexes some

complexes

Cu+ with

to the

data

[113].

and

regard

to marked

literature

similar

been

with

owing

in.solution

forms

of Agf

thermodynamic

the

constants

(56)

acid

anthracene-[116]-(AgC104)4

Referenceso.452

log

measured

structure

trifluoromathanesulphonic those

acetylene CZC

[llO]_

RhAg2(CZCC6Fg)5(PPh3)3,

essentially

acetylene

olefins

observed

Formation

have

the

been

observed

contradictions

chelate

the

comparing

[112].

three 2.25x,

formation

has

of

trends

alcohols the

the

monoolefins

when

of

afforded

the Ag

were

11111.

for

parameters

be marked

values.

data

to

2.34&l%C

carbon

yields

crystallographically and

which

and &4N[Ag(CN)2]

in quantitative

resolved

Rh-P

K2[Ag(CN)(SCN)2],

halides

Ag(CsCC6F5)

asymmetrically

were;

and

Alkyl

octahedral

2.60-3.13i

of liquid

of structural

with been

to nearest

Thermodynamic

[lOS].

isocyanides

of RhCl(PPh3)3

structure

Ag

K[Ag(CN)(SCN)]

analysis

corresponding

Treatment the

to form

The with

influence

changes

These

in ASo

increasing

alkyl

of several

silver

olefins salt

aromatics

of naphthalene-[1151

completed.

may

for desolvation

of the

a

structures

of to

(57) are

(55)

x--

.Lg--_OyH

(CH2),,/ (56)

very similar and comprise of parallel sheets in the order -aromatic-AgC104H20-H20-~gC104-aromatic-.

The sheets are made up of two AgC104 chains

held together by wez~k Ag-0 interactions and Van Der Waal's naphthalene Ag-C.bonds

is associated of

2.62,

with

four

different

hydrated

Ag

forces. ions

with

Each equal

and the compounds are best described as arene'clathrates.

For (CF3COOAg)2C6Hg the molecule comprises-of parallel l&ear

chains of

metal~atoms with alternating short and long distances of-2.9

and 6-81L

respectivel$.

Novel features of this structu&

are:planar

3-coordinate :

2.

433

._.

--o

(5.71

oxygen atoms and a silver atom; two different geometric configurations the Ag ion .in the same structure, and bridging

IV

Catalysis _^^^^^^^^ A series

by silver ^^ ^^^^^^

salts ^^_L^

of papers

has

of the

on

the rearrangement

tricyclo[4.1.0.02'7 1,2Lhydride

suitable

and

constructed

Referencesp.452

side

(58-59)

[117].

rearrangement

of

From studies [118-1201 on effects of structural mechanism

1heptanes alkyl

ligands.

appeared on the Ag+ catalysed

strained carbon-carbon bonds. changes

benzene

for

shift chains,

it was

in the AgC104 shown

to an argento competes

that,

promoted with

carbonium

favourably

Cl

ion with

isomerisation functionalised, centre, migration

from of

(59)

I

.. :: !..

'.

&s'aixyli& :

cycloherene

the exl;iuslve -as the

that

effects the

at

the

mechanistic

diversion

8, yor

6 pathways

is further

distribution

from

via

conformational

3-position,

was

in operation,

of

the

the

and

isomerisations

from

served

(scheme

13)

(Scheme

of

the

Y-rearrangement

AS+and or c-d

the and

strained ultimate

a-rearrangement, bonds the

flanking

[119].

of R and

reaction

of Ag+

by Ag+

with

with

c--d

a bimolecular

(scheme

above [120]

(60) by As+

position

The

the

mechani;Sm

minor

competitive

shift

postulated

9,10-diazobasketanes

the nature The

1.2-carbon

C7 was

indicated

cleavage

13)

involving

an attack

consistency

to demonstrate

cleavage

is consistent ring

stereo-

substituent

major b-c

partitioned

The

tricycloheptanes effects,

from

ensuing

(Y-pathway).

isomeric

influence

regioselectivity

with

at Cl is increased,

of bicyclo[3.2.0]hept-6-enes

product

a secondary

The

[118].

to the

substituent

formation

of isomeric

hydrogen

p-rearrangement

bulk-of-the

.specific

435

-.

...

the

edge

14)

attack

C1203.

plane

(scheme

reaction

The

to 9,10-diazosnoutanes

of substitution,

particularly

(61) gave 1,3-cyclohexadiene

at bonds

To account

defined

15).

between

by

the

b-c for

two

edge-

rearrangement was for

the

of

sensitive

to

R=CN [121].

[122], and with bicyclic

organoboranes to give a mixture of monocyclic ketone and &s-monocyclic olefin.. 11231:

References

In the An

ionic

p_ 452

latter

case

mechanism

a diradical appears

intermediate

to operate

for

the

is proposed Ag+

(scheme

isomerisations

16)

(Scheme

14)

C

1

R, =

electron donating

(Scheme151

of quadricyclanes

(scheme 17).

The study, which compared the various effects

of Rh(1). Pd(II) and Ag(I)..showed 21

cases the sole'product is (62)-

.%

that'-with Ag
:

.’

(60)

(61)

0”

-

+ (-J

ti (Schkme

16)

L&-EAq+-g&E;:?&qzzE-hE Ag(I) KU) (Scheme

References

p_ 452

17)

(62)

.__

438.

. gave

a mixture

alkoiyl

of isomeric

group

philicity

ionisation-process

has

appiicatjons

&d&s

been

studied.

(scheme

19)

were

of

.

.. : ,

:

._

(63) -[124,]. .-Th~.Ag(I)--promoted

in neutral

~_ :-.~ _ :.

solvents

$fechantstic-aspects discussed.

_'

.. -. .

-of negligible

(scheme

'f in dry Ag

nixleo'.

18)' and .synth&ic

benzene

Was

found

....-

to-

E'

(63)

pJD

:

Ag+_

_*g+_MJ$

& D Ag---OCH,

(Scheme181

Et0 Me

\ /

CH

H

I5 (Scheme

Et0

19)

-.

‘. ..

be an exceedingly in benzhydryl the

silver

mediate

mild

ethers

ion

method

for From

[125].

assisted

cyclopropyl

removal

the majority

solvolysis

cation

of benzhydryl

of

the

blocking

of products

compounds

(67) or a partially

obtained

(64-66),

opened

groups

an

species

from

inter-

(68) Late

6+

f Y (64)

(65) Br

Er

Br

&

%

2

I (67)

'

(68)

/

(66)

proposed [Ag(CF with

3

The

[126]_ COO)]x

has

benzene,

bicyclics

2-methoxyallyl

been

to react

p-xylene

toluene

(scheme

shown

cation

21)) [127].

and The

generated

under

remarkably

mesitylene

heptene

from

the bromide

mild

to produce

(69)

gave

by

conditions

a range

(70) with

of new

Ag(1)

salts

[128].

The (X=C104,

use

of benzene

Triflate)

as an effective perchlorztes alkyl The

variety'-of

alkyl

selective

or triflates

halides

r?ute

with

as solvent

was

by promoting found

organic

Referencesp.l52

for

iodides

synthetic 11291. the

procedure

AgBF4

removal

to the

substitution

inhibited

to be a convenient halides

the

isomerisation for

forming

facilitates

of

the

the halide

technique

corresponding

reactions

for

as the

carbonyl

and

simple

DMSO

of AgX was

primary

oxidations

insoluble conversion compounds

used

of

AgX. of a under

+

?Me

.:

w H+I -1

+OMe

/

I-H+

7

OMe

-

I;

-

‘1

U

I

-MeX -MeOH

1

-MeCH

(catal 1 H+

(Scheme201

(69)

(70)

tild

conditions

for

highly

[1303.

Ago

in acetone~solutions

is an excellent

catalyst'

.-

methyl

alkyl

selectiive ketones

Anti-Markownikov in

73433%

yields

additions, via

free

giving

radical

straight pathway&

chain (1311..

._

-.

_. - _Dir&t

441 &idence

that complexation of a carbon bonded halogen with Agf

can be followed by a reaction in which the halogen migrates from carbon to carbon has been obtained. -.

Thus 3-chlorobut-l-ene with AgC104 in XeCN

gave, as well as the usual products, a mixture of cis-.and trans-but-2enyl chlorides

[132]. (71) underwent cycloadditions

in CH2C12 at -603 with

various 1,3-dienes in the presence of AgBF4 to produce

i! =

&CH,),BF,-

Cl

(72-76) 11331.

R

/ 6P Z

(72)

R =

H

(73)

R =

Me

2 ( 76)

The Ag+ assisted solvolysis of (E,Z) and (Z,Z)-PhCCl=CHCH=CBrPh

in AcOH

and the (E,Z) isomer in Ac20 gave (E,Z) and (Z,Z)-PhCCl=CHCHCPhOAc (Z)-PhCCl=CHCzCPh respectively. postulated

[134].

and

The intermediate chloronium ion (77) is

Cyclohexene was treated with equimolar amounts of

_-

.

.: .:

-442.:-

:

__

-_

1

.-.

1,

:

.-

-.

‘T,._

.-

:.

-. _.-.. :-

. .

-CsH5CH20AgI

'and.AcOAgX

cyqlohexylene

and

c1361. by

the

of.the

V

gave

the

._

in -anhyd.r.ous-sbIvent+

in A&OH-H20

_te give

product

with

X=NH2. F and

and

l-(N-alkylformimidoyl)imida~oIes AgCl-catalysed imidazole

and

Cold-carbon ^^_^^__^ A review

complexes MeCOCHZCOMe

of.alkyl

triaaole

.&th

.~_ :. <.

&i3,NaF.iAgCN

~...

(48-82%)

&

ONCF2CF2NC0

-triazole&

(32%)

prepared

were

isonitriles‘into

respectively

:

the

N-H

,.

--

bond

[i37].

bonds _^_^^

with

has

insertion

:.

give-tra&l,Z-~.~.

(X=Cl) CN

: .._

of~predominately:the

dials

The~reaction~of:ONCF2CF2CCX

[135].

NaN3

and

esters,

KS-isomer

'(X=Br,I)

_

;

:-

48 refs.

appeared in the

on the

preparation

The

[138].

presence

reaction

of kg20

gave

and

reactions

of AuBrPPh3

of organogold

with

MeZCO

MeCOCHpAuPPh3

and

in a solution

of MeCN,

or

MeCOCH(AuPPh,) >

COMe

11391.

Choro(l,4-oxathian)gold(I)

dimethylpyridine form and

and

Et3N

Au2C20.(2,6-Mepy), PhCPCH

gave

R4N[R'AuX3] actions

under

which

[AuCECPh]

and

(R=Et,n-Bu;X=Cl,Br).

attack

the

species,'is

carbon

21.

series

of- papers

products

two

new

and

AuC13

on heating [140].

gold

11491.

the~unusual

complexes (79)

of

COTAuCl

Displacement:of

and

in which

[144-1481

and

been

and

COTAu2Ci.. A&Cl

the

were

with

in

produced. obtained

by

11431.

protonation

determined

i

nucleophilic

AuClPPh3

R4Au2Cu2

from

has

CO from

with

were

inter-

gold(II1)

in Et20,

gave

obtained

species

hydrochloride

to the

to

Au2C20

from

compounds

(78) with.CuBr

appeared

25".

obtained

on

of HBF4

cluster

(R=Cp,R'=H,M=Fe) complexes

were

ketene

arylgold

of Ph2C=CHMgBr

products

have

to

intermediate,

on addition Cold

with

The

to the nitrogen

Treatment

which

reaction

on

olefin

A nitrene

[142].

Further

organogold

the

reacted

phenylhydraaine

bonded

[141].

Ph2C=CHAupPh3,

scheme

of

atom

proposed

[Ph2CfCH(AuPPh3),]BF;

with

Au2C20

acetanilide

or substituted

R4N[AuX4]

THF'gave

gave

at -lo",

(R'=Ph,p-ClC6H4,p-BrC6H4,p-N02C6H4)

of phenyl

by

argon

2,6-

A reactions

structure

of one

[147,148]. obtained

The

from

2,4,6_triphenylphosp

. ..

.-

COT

or

( R4Au2Li.$

. (78)

R;Hg

MeauPPn3

+

H3Fd

.=f’= C,TI~F~, C~FeeC,k~~x; X = (Ref.

I

37. r.feO,c

146)

HBFJ = M=

CPFK~H,AUPP~,

H.CI.Me0.Me2NCH2

R’=

Fe.R

a = cp M = Fe

=

Cp

(Ret. 147)

ii

i

(79) R’= M = R =

H

A

Mn

cRef.lr5)

H3FS

HB!=a

(CO&

(C!+=CH)AuPPh, AUPPtY3 W.:l70,

@ !

i Mrl

(Ref. 144)

mxocii2~~PPn,

oc i o&1 \ IL =

habenzene

or Ph2Zn

tively.

Benzenethiol

platinum

by

with AucIV)

a free

methylgold(II1) would

be

1:lcomplexes

cleaved radical

the

chain

proceeds

involved

eisLtrm2s-rearrangement with

gave

in and

by the

CO.PPh>

[SO] metal-C

bond

Ph3AuZn

(80)

11511

in methylgold

and

mechanism.

A similar

but

a different

mechanism

presumably

radical

reductive

process elimination

RMe2AuPPhg(R=Me,Et,Pr,Me2CH,bie3C,Me2CHCH2).

Referencesp.452

and

11521.

Alkyl

reactions Rates

slower

respecmethyl reaction because

isomerisation,

were

of alkyl

observed isomerisation

(79)

and

reductive

elimination

a dissociative by PPh3 hedral

additions gold(II1)

TIX'(C6F5)2 The

mechanism.

products

and

of

AuX(C6F5)L

complexes

cis-fmns

&as

were

retarded

Rearrangement

a unimolecular

intermediate,

(X'=Br,I)

these

process,

. .

gave w&k

tetra-

additions

AuX(C-6.) ._ 652.

also

: of

L.

characteris_&

.. cl541

:--.

.. :

: ;:

a

Oxidative

.. 1 ._

unaffected

invdlv+g

L=P&i,AsPh3)

(X=C6F5,Ph,No3.0hc,SCN,PPh3)

PPh3..indicating

relatively

possibly

suggested~[i53].

to.AuXL(X=Cl,Br;?;

was

by

: .‘. ...I._. : .:_. .. .- _.. ._ .:-:

:

:I _ . .:_,:.

.. I 1:: .:

.-. -‘._

_

_.:_-1

~-:

Oxidative

445

-_

_. -:. additions.of

: MeI:to

MeAuL(L=PPh3,PMe3)

follow

a multistep

.: -mechanism

for-L=PPh3,giving

exchanges.

furtherl'with

elimination ~: gives,

to C$i6

elimination. Me2AuIPMe3 species

in high

were-also

reacted the

with

stable a slow

studied

complex HO(CH

isocyanide

give

) NC 2n

to give

IAuPPh3.

The

Me3AuPPh3. The

Me AuPMe

3

reaction

does

AuIPMe3

additions

gold not and

isocyanides

to other

and

with

AuL2PPh3 (n=2,3) the

amines,

OMe

I Au

Me0 (84)

Referencesp.452

reductive

occurs,

alkyl

producing

gold

cation

the

electron

11563. to give (831,

rich

The

olefin

gold
(82),

which

isolated

as

(81)(=L2) anion

further the

reacted

BPh4

AuCli

produced

R=R'=Me).

The

the bis-carbene cyclic

product

gave

AuCli

salt

(83)

OMe

MeN

(L=PMe3)

[155].

(NR’H)I~ (R=H.R'=Me;

Au[C(NRR')

complex

Me1

formed

reductive

undergo

(81)

With

Me2AuIPPhj

undergoes

reactive

which

3’

initial

which

more

with

Oxidative

yields.

of AuC1PPh3

the his-carbene

and

andlMeAuPPh3-

Instead

Treatment

MeI-to

a more

however,

C2H6

complex (84)

is

with 11571.

446

-._.

.

.

-.‘._..

.

..,._

-.

.;

, __,_

-__. form&from

reactioqsof

AuClPPh3,MeNC

-..

(

.‘..~‘-_:_.-~.:

-

:.I

.’

::

and:methanoi; .and-undergoes.'

--.I

_: . . .. AuCC(NHMe)NEfe21~and CHNM~?(~~~O)~IAIIC~ yield HC([email protected], HC(NMe)N(fie)2~ cl&&&%

by~HC.1

[HNM; (MeO)C]AuCll

t.6 give

:

The.carbenk;.Au~d(~e)~~;j

and HC(OMe)NMe respectively with CN- in.Me2S0, whereas the diamidide MeN=CNNMeCH=NMe

is the result of MeNC and AulC(NNMe)2]~ reactions.

These

ligand displacement reactions establish carbene complexes as.intermediates in the a-addition of protic nucleophiles with isocyanides. 11581.

The

reaction of AuClL(L=Me S PPh ) with an isocyanide and KOH III alcohol gave

2'

3

I(RO)(R'N=)CAUI~.which was also obtained from the reversible deprotonation reactions of the carbene complexes proposed for the trimer

[(RO)(R'NN)C]AUCL.

(85) 11591.

is

.The structure

The organic product (p-MeC6H4NH)2C0

is the result of stirring a 50% aq.Me2CO

solution

trans-[i(p-~feC6H4NH)2C]2Au12]C104

in air

[160].

R'=

Me;R

of

=

the

carbene

complex

Et.Me.CH,Ph.CCHll. p-MeCCH,

/

N-Au-C

//

R'=

M+CH;

R =

p-MeCCH,

I

(85)

VI

Complexes of general dnterest --^---.~~- A_ ______I 11-1111.. A review,

of Pd,Pt,Cu,Ag and

PPh

occupies

3

with 66 refs., of phosphine- an.d arsine-olefin complexes and Au has appeared

undergoes an

axial

structural or basal

11611. The 1:l adduct of Cu(Hfacac)2

isonerisation

coordination

in-which ._

position

[X2]..

: :

‘-.

the.PPh 3-.ligand

.-

new

: -.

.. . ..

-.

The

;

..

:

_-

447

: ~phosPhite-tyPe-complexes~AgC1(P(OEt)Ph2]2, R=MeiEt 116311, AuXL[X=Cl, E=P(OEt)Ph2

AgClL

[L=P(OMe)Ph;?,P(OR)Ph ?' [163];X=C1,Br,L=P(OCB2)3CEt[164]],

~[AuLL']~C1O4[L=P(OCH2)3CEt,L'=MeCN;L=L'~?(OCH2)3CEt[164]], P(OCH2)3CEt[164]:~M=Cu.Ag.Au,L=P(OR)3[165]:

[ML4]C104[M=Au,L=

P(OR),Ph,P(OR)Pbn,[l66]: R=Me.Et]

:have been prepared by either ligand displacement reactions in polar solvents or by reaction with metal halide or olefin complex in a suitable solvent. The non-conducting phosphinoethylene, [167].

compounds [(AgN03)RL] (L=DPE,DPM,cis-1.2-bisdiphenylo-phenylenebisdimethylarsine)

have been synthesised

The sign and magnitude of tz~~ns-~Jplp in [Au(PMe,),]+ have been

recorded by the 1B{31P] INDOR technique 11683.

IR, far IR and Raman spectra

have been measured for the complexes NiL(C0)3, AuXL(X=Cl,Br,L=PPh3,AsPh3) [169], R4N[AuC14][170]

and AuXP(4-FC6H4)3

parameters tabulated.

AuC13L

Refez?ncesp.452

(X=Cl,Br)1171] and the various

(e.g. L=PhCN, p-MeC6W4CN,PhCH2CN)

products

449 -&a&ti~oievaat : -2$.Au-P

Parameters

.2.33&

observed

P-A<+

[Ni(S2C2(CN]2)2]

(88);

2.27,

2.74i;

2.21;

(terminal);

far

.&

Ag-P

0.1-p 2.195;

2.305i

(bridging)

Cu-P.2.19i

11831

(viii)

CU-P

2.20;

[184]

&-I

2:68x;

no

CU-P

predictions

(ix)

(iv)

[181]

(vi)

(vii)

(93)

2.36:.11851. as

to why

11781

Cu-Cl

(92); and For

"cubaue"

(90) (91),

2-38

Cu-Cl

(bridging). Cu-Cl

2-19i

2-4i;

- 2.66i: (93)

tetrameric "chair

[Ag(PPhS)2]2

Cu-Cl

(CuIAsEt3)4

or

2.30x

(89);

2.32;

Cu-Br

the

Cu-P

(iii)

(CUC~)~(DPH)~

(CuClPPh3)4

(M=P);

Au-Cl

(87);

Ph4P[Cu2C16]

(CuBrPPh3)4.2CHC13

be made

2-32

(v) Ph4As[Cu2C16];

[182]

CU-As

CUBF~(PP~~)~

Cu-F

11791

(CuIPEt3)4

2-25;;

could

2.48i

145"

(tern&l)

(ii)

observed].

[180]

Cl-G-Cl

(i) AuC1(PPh3)2.C6Hg(86);

[177],

132.1"

:ffon~=est.Cu-P-distances

are

(N=As);

structure

structure"

is

preferred.

A review salts Pd,Pt>

with

on metallation

Ag,Cu,Pb,Hg

with

%fei-encesp_ 452

NaBH4

and

and

reactions Tl

NaBH3CN

[1863. has

been

of organoboranes The

reactions

studied

and

focuses

of MC12 various

on

their

(N=Co,Ni,Cu, products

were

(90)

(91):

:

_-.

:

. .

M

M

(93)

(92)

.o

w

cu

0

BH

References p_ 452

(94)

0cu

complexes

points X-ray

[lss]_-

to a doubIe.H-bridge

determinations

fo:r:.& .and a singIe.H-bridge.for

on n'-bfs
Ag

tetrakis(triphenyl-._

i-

. ..'

phosphine)dicopper(I).

[ISS],

(HBpz=pyrazoylborate) proposed occurs

that via

[191]

covalent

3-centre

bonds

hybridised

atoms

[Cu(HBpz3)]i

a green

paramagnetic

ha&

of

:(94). [190]

and

been-completed;

interaction

tetrahedrally [190].

Cu2BlOHlO

of

the

sp hybrid

Cu(1)

CU atoms

Cu(I),lith

interaction

takes

substance

up one

of

For

formula

with

tiith the

mole

Cv2B10H10.it

B-B

02

Cu2(HBpz3)202

hgs

the

borage

edges,

or a

four

of dry

.’

.[Cu(&3p+,)]2_(95)

nearest

been.

aggregate

boron

irreversibly

to-give

[191]_

References ^^^___^_^^ T. Ikariya

and A. Yamamoto,

N. Marsich

and

T. Tsuda,

T. Nakatsuka,

G. Nardin, (1974) 5

H.

6

J-W.

A_Camus,

L. Rarrdaccio

.I. Organometal..

Chem.,

J. Organometal.

Chem.;

T. Hirayama

T.

and

and

E. Zangrando,

72

81

(1974)

(1974)

Saegusa,

87.

Chem.

J. Organometal.

154.

Commun; Chem.,

(1974)

557.

74

C23.

Scbmidbaur, Fitch

and

3. Adlkofer C.A.

4 (1974)

1.

D.A.

Leirsburg

Van

G. Cipriani

T.Tsuda,

H. Habu,

(1974)

Heimann,

Chem.

Syn.

Reactiv.

Inorg.

Kettner,

and

P. Kock,

and M.

C.W.

and

De Kock,

J.. Phys.

E..Perrolti,

S. Horiguchi

and

Ber.,

Metal-Org-

Chem.,.78

Gazz.Chim. T.

107 (l974)

Saegusa,

Italia,

3697.

Chem.,

(I974)

134.

104

(1974)

J.~Amer.

Chem.

Sot.,

9 (1974)

95.

599. 96

5930.

10

F- Bonati

11

R.W.

and

Stephany,

G_ Minghetti, M.J.A.

Inorg. and’

DeBie

Acta,

W. Drenth,

: 6 (1974)

Chim.

Org.

Magnetic

-.

Resonance,

._

45.

:

-.‘ _-

.: ~._ .-.

-z_ :. ._

.-.

._

._

:

.

/:

..-_: _-__z--_

453 :

.I2

R.G. .&lo_mon _-

13

J. Evans

14

Yu.

Yu.

Y-Y

17

and J.R.

Belarus.

Norton, N.P.

35.

Tatarintseva

Navuk.

and

1-M.

Roev,

Dokl.

80(1974)

J-M.

BrQgeault

and

G. Pannetier,

18

P.F.

Rodesiler

and

E.L.

19

H.F.

Efner,

J. Fluorine

20

M.B.

Dines,

Separ.

21

T. Tsuda,

K. Ueda

22

R. Clark,

J. Howard

23

M.R.

Churchill

and

24

0-M.

Abu

and M-1.

25

G. Van

26

M-1.

Koten

Bruce,

Chem.,

64

and

Abu

(1974)

V-S.

Myl'nikov,

28

L-V.

Konovalov

C.A.

81(1974)

Zh. and

70316s

SO(1974)

Beloruss.

SSR

18

Chem.

Sot.,

584.

France,

(1974)

(1974)

2370.

599.

114.

661. Chem.

Bezman,

Commun.,

JCS

Inorg.

Bruce,

(1974)

JCS

Chem.,

Dalton

Chem. R.E.

Dalton

(1974)

and

380.

(1974)

2027.

13 (1974)

Commun.,

Davis

(1974)

2302.

(1974) N.V.

1418.

575.

Raghaven,

J. Organometal.

Strukt. V.S.

Khim,

Myl'nikov,

15(1974) Zh.

244.

Strukt.

C.A. Rhim.,

81(1974)

12677m.

15 (1974)

iG9.

168802j.

31

R. Jungst

32

M. Wicholas,

33

G. Nord

and H. Matthes,

34

Y. Ito,

T. Konoike

35

E-C.

36

J. Klein

A. Turco, and

and

and

Akad.

C48.

D.M.

Ashby,

Veotsi,

C.A.

Nauk.

Commun.,

P. Woodward,

Salah,

30

Duggan

8(1973)

Noltes,

P.

and

23.

Commun.,

4 (1974)

T.Saegusa,

29

Rigo

135.

3042.

Erofeev,

(1973)

Bull,

Chem.

Chem.,

S.A.

B.V.

Akad.

Chem.

Amma,

Sci.,

J.G.

0-M.

27

Mainwaring,

and

(1974)

(1974)

125317s.

D.E.

and

13

and

Rhim.

and

Salah

Chem.,

Ser.

C.A.

Huang

Inorg.

64

Chem..

J. Organometal.

SSR;

S. Mardashev

(1974) 16

J-K..Kochi,

S_ Mardashev,

N&uk. 15

and

D.N.

Coord.

Hendrickson,

G. Stucky, and

T.F.

Chem.

Inorg_

T. Wolford,

and

Acta T.

R. Levene,

Chem..

Inorg. Chem.

JCS

and

13

Inorg.

Saegusa,

Korenowski

Rev.,

Chem., 13(1974)

Chem.,

Schwartz, (1973)

1911.

2404. 316.

28(1974)

Tetrahedron

II,

133.

13(1974)

13(1974)

Stand.,

R-D.

Perkin,

(1974)

Letters Chem. 1971.

13. (1974) Commun.

1287. (1974)

157.

R..Bausch,-B.

f;. Dreeska&‘and

Bogdanovic,

:

J.R'~Ko&&;:A&.len -

I625:

..' .:

.< :

39

N.

Finch,

R.T.

L. Blanchard,

Puckett

and

L.H.~Werner,:~J_ . .

39(1974)

=

(1974):

-.

--

1.

1' . ..

.Org.--Chem_,

:

.-

1118;

40

J.W.

Patterson

Jr.

41

R.K.

Boekman

Jr.,

J. Amer.

Chem.

Soc_..95(J.Q73)_

42

R.K.

Boekman

Jr..

J. Amer.

Chem.

Sot.,

43

E-J.

Corey,

K_C_

and

J.R.

Fried;

and

Nicolaou

J..Org.

D.J.

Chemi,-39(!974) 6867.

96(1974)

Beemes,

2506..

6179.

Tetrahedron

Letters

(1974)

2439. 44

3.X

Normant,

C.R.

45

M-E-

Lewellyn

and

46

U. Revid

.47

and

G. Bozzato,

48

E.C.

49

J. Klein

50

J.C.

51

D-S.

J-P.

and

Sci.,

and M.

G. Hei‘nsohn, R. Levene, D.

C, 277(1973)

J. Org.Chem_.

J.Org.Chem.,

Bachmann

Blazejewski,

Ser.

Tarbell,

R. Iken,

Ashby-and

29(1973)

Acad.

39(1974) Pesaro;

J_Org_

Tetrahedron

Cantacuzene

1755.

2637. Cormnun.,

39(1974)

Letters and

39(1974)

Chem.

C&em_,

1045.

1005.

3297.

(1974)

C. Wakselman,

(1974)

2935. Tetrahedron,

4233.

G. Linstrumelle,

Krieger

J.&

and

G.M.

Whitesides,

Org.Synth.,

53(1974)

1842. 52

J.A..Katzenellenbogen

53

J.F.

Normant,

(Paris) 54

A.G.

278(1974)

IO(1974)

Crumrine,

C. Cahiez

A.Commercon,

Muradyan,

Khim:,

and A.L.

N.M.

S-M.

Morylan,

J. Villi&as,

1122.

C.A.

Gabrielyan

81(1974)-

49193b. (1974)

H.

Suzuki

and.T.-.Hanafusa,

Synthesis

56

T.

Cohen,

J. Wood

Dietz

57

G.M-

96(1974)

Chem.

Soc.,.96(1974)5662. C.R.

Acad.

SC.

967.

55

Wnitesides.

and

J. Amer.

and A.G. J-S.

Sadowski

Jr.,

and

and

Sh.0.

Badanyan,

Zh.

Org.

53.

Tetrahedron

J; Lilburn,

Letters

(1974)

J. Amer.; Chem.

3555.

Sot.,

2829. -_

..

-: :-:_:.

:

455 _' 58

MiP.. Periasamy.&d

i9

-K. Oshima,

60 ~61

H.M. Walborsky, J. Org. @em.,

H. Yamamoto

I.. Kuwajima, K.

and

Sugimoto

H. Nozaki,

and

Chem. Sot., 95(1973) 7926.

J. Amer.

T. Murofushi,

39(1974) 611.

Chem.

Letters

625

(1974)

J.R. Bull and H.H. Lachmann, Tetrahedron Letters (1973) 3055.

62

J;R; Bull and A. Tuinman, Tetrahedron Letters

63

C.P. Casey and D.F.

64

M.C. Baird,

65

S_ Kobayashi-and T. Mukaiyama, Chem. Lett. (1974) 705.

66

B-M,

Trost,

67

J-F;

Knifton,

68

W.

69

R. Baker and D.E. Halliday. JCS Perkin,

70

J-Y. Satoh, C.T.

Tetrahedron

Marten,

J. Organometal.

T.J.

Dietsche

J. Catal.,

Strohmeier,

Chem.,

and

T.J.

33<1974)

2. Naturforsch,

Yokoyama.

(1974) 92.5.

Letters

64 (1974) 289.

Fullerton,

J.Org_

Chem.

39.(1974)

737.

289.

B, 29(1974)

A.M.

(1973) 4249.

282.

II (1974) 208.

Haruta, K_ Nishizawa, M. Hirose and

A. Hagitani, Chem. Lett., (1974) 1521. 71

1-G. Malykhina, M.A. Kazankova and 1-F. Lutsenko, Zh. Obshch. Khim. 43 (1973) 2790. C.A. 80 (1974) 70918f.

72

M. Iwata

73

J.S.

S. Emoto,

Grossert,

Letters 74

and

Chem.

J. Buter,

Lett.,

E.W.H.

(1974)

Asveld

959.

and

R.M.

Kellogg,

Tetrahedron

(1974) 2805.

M.I. Katsin, Yu. N. Ogibin and G.I. Nikishin, Izv.Akad. Nauk SSSR Ser. Khim. (1974) 139. C.A. 81(1974) 3129g.

75

L.A. Akopyan, 1-S. Tsaturyan and S.G. Matsoyan, Zh. Obshch. Khim. 44<1974) 1838

C.A. 81<1974) 13539Ov.

76

A-A_ Moroz and M.S. Shvartsberg, Russ. Chem. Rev., 43(1974) 679.

77

H. Hayashi, C.A.

H. Nishi

and

K. Kawasaki,

Nippon

Kagaku

Kaishi

(1973)

1949;

80(1974) 26405-h.

78

T.

Cohen,

R.J.

Lewarchik

and

J.Z.

79

J.

Chodowska-Palicka

80

G. Fouquet and M. Schlosser,.Angew

Tarino,

J. Amer.

and M. Nilsson, Synthesis,

Chem.

Sot.,

96

(1974)

(1974) 128.

Chem. Intern. Ed. Engl.

13(1974)82.

7753

456

: .-

81

A.Onoe;

82

H-L_

-. ... ..,; .:

..

.I_ :___I.

.-';:~:':_.:',r_:I.: ::_;;_l-. :::-_-;;._..; j

ja?-g,yt

S.Uemura;

Elbe

--: -1‘

and:M;Okauo,

G. Koebrich,

and

Bull.

Chem. 107_

Ch&.

:(1474j--.1

A.

84

P:Piccardi,

85

R.A.

Lynd

86

L.P.

Yur'eva,

87

A-

88

R. Levene;

89

E.G.

Derouane,

90

L.A.

Akopyan,

de

Heijere,

Sevin,

2233 91

Staab

93

F. Bohlmann

94

A.E.

J.Y_

J.N.

V-A.

Nofedov.

97

A.G.

Muradyan,

Badanyan, 98

A. Or,

99

A.K.

D-V.

K.A.

C.A.

M. Levy,

661.

C-A.

69941b.

Chem.

Chem.

--

'.:

440.

..

(1973)

SS(L973)

Sot.,

France

Chem..

807.

Zh.Org.

(1974)

.67 (1974)

Phys.Letters,

and

(1974)

107(1974)

and

G.A.

25

Khim.

S.G

9(1973)

Arm.

424. 2115. Arm.

Khim.

K. Giyasov

and-D.

Karapetyan 81<1974)-

43(1973)

F-G.

Kamaev,

Zh.

145352~. 2016.

80(1974)

Vofsi,.JCS and.G.A.

C-A_

80(1974)

M.K; Mordoyan

Morlyan,

C.A.

and

3288n.

and

Sh.

0.

59360x.

Perkin,

-II; (1974)

Chukhadzhyan,

Arm.

857.

Khim

Zh.

151379d.

Dorfman,

'Electrokhim,

Z.F.

Prazdnikova

Akad.

N&k.

Kaz.

and

I.V.'Rodnikova,

SSR,

4(1973)

92.

913.

467.

(1974)

Matsoyan,

Chukhadzhyan,

SO(1974)

N.M. 21.

'

;..__;. :

121365h.

Ber.,

C.A.

Kbim..

:

:--:.

151485k.

Gabrielyan,

Ya.A_

Tsaturyan

Tadzhimukhamedov,

M. Asscher R-G.

Chem.

81(1974)

Arm.,

Katal.

__:I‘

..

658.

Matsoyan,

Synthesis

Kurginyan

Obschch.

S.M.

Sokol'skii,

80<1974)

80(1974)

lO(1974)

Prom.

Tr.Inst.Org.

743.

J. Kocur,

Zh_

'~ '

-. (Milan);

J. Organotieiai.

S.G.

1-S.

S. Kh.

Kurginyan,

27(1974)

and

Ovakimyan,

C.A.

A-D. Grebenyuk, -. Zh. Org. Khim.

I

48.

R. Hubin,

K. Neunhoeffer,

668.

_-., _-

_,

14531011.

E.V.

and

(1974)

J. Klein, and

_

Ind-

P. Cadiot,.Bull-

Grigoryan

SO(1974)

96

and

Braham

S.G.

and

and

-;

-(1974)_306;

Annalen, Chim-

f&em.. Rev.,.43(1974)

Becker

Kalaidzhyau,

27(1974)

Synthesis

Chodkiewicz

26(1973)

B.A.

100

Russ.

F. Heinrich;

P. Messardo,

G. Zueifel,

L.A.'Akopyan,

92

95

and

N_

Zh.

and

M. Mod&a-and

C.A.

Khim.

Lzttke

W.

6'~11;-:

:

Ber:;. ._

83

: f_;_~ ..

7;;&) _.j& .&A ._.-_ - :

S&z.;

C.A.

243.

. : ._ .StM;:.Br&lbvakii, ‘X01 : .I : Kinet.:Katal., -102

103

L.G..Bruk, 14(1973)

.1222.

Badanyan

and

C.A.

Sl(1974)

77382f.

104

5.3.

Kim

105

A.P.

Manzara

106

T.-Cohen,

and

O.N.

and

and

R-M;

Flid,

364752.

and

R.M.

Flid,

Kinet.

Katal.

24727r. Ar.

Chem.

P. Kovacic, T-M.

80(1974)

Temkin

Stepanyan,

T. Takitawa,

G. Herman,

96(1974) G.M.

A.N.

Kostyushin_,_ O.N:Temkin

C.A.

_C.A. 81(1974)

S-0.

107

A.S.

.. .L.G.,-Bruk,: S.M. Brailuvskii, 15(1974)'516.

457

.

Khm. -

Commun.,

27(1974)

(1974)

J.Org.Chem.,

Chapman

Zh.

356.

39(1974)

and

D. Kuhn,

and

P.E.

288.

504.

J.Pmer.Chem.

Sot.,

5627.

Whitesides,

D.E.

Bergbreiter

Kendall,

J.Amer.Chem.Soc..

96(1974)2806. 108

E.T.

Blues,

(1974) 109

N.A.

111

L.B.

Sergeeva, C.A.

D-1.

255.

O.M.

Salah,

and

I.W.

Lawston,

Chem.Commun.,

and

A-V.

Mazepa,

Zh.Neorg.Khim.,

18(1973)

M.I.

and

Bruce,

.I_ Songstad,

M.R.

Churchill

Acta

and

Chem.Scand.,

B.G.

De

Boer,

Ser.A,

Chem.Commun.,

688.

112

G-S.

Natarajan

113

M. Novak, (1974)

Irwin

55423x.

A. Martinsen

28(1974) Abu

Semenishin

80(1974)

Engemyr,

(1974)

J.G.

.466.

2956. 110

D.Bryce-Smith,

and

D.A.

K.A_

Aikens

Venkatachalam,

and W-D.

Aust.J.Chem.,

Clossen,

Inorg.

27(1974)

Nucl.Chem.

1209.

Letters,

10

1117.

114

M.B.

Dines,

.T.Organometal.

115

E.A.

Hall

116

E.A.H.

117

G-W.

Hunt;

118

L.A.

Paquette

119

G.Zon

and

E.L.

Griffith

and

T.C.

L.A.

Amma,

and

E.L.

Lee

and

and

G.Zon.

Paquette,

Chem.,

67(1974)

J.Amer.Chem.Soc., Amma, E.L.

C55. 96(1974)

J.Amer.Chem.Soc.,

Amma,

743.

96(1974)

Inorg.Nucl.Chem.

5407.

Letters,

J_Amer_Chem.Soc_.

96(1974)

203.

J.Amer.Chem.Soc.,

96(1974)

215.

lO(1974)

909.

-458.. .x20:

.I21

1 _ .,::..

...

:

L.A;m,p&ette

.&d

.-..

.G.Z&;

I.

L.A..Paquette,'D.R.

., I, : _. .: ” ...-i._-:_:.~_;-:‘_~. :1 __- yz_: :. :____..: -/.;-; : ‘, .. . -,~;Amer.~em.Soc.;:.9~.(1974~. i&l

:

..::

._ : :

1.’ :

_.:

Chem.Ber;,~i07(19~?i)'3908; _- -. I

..

M. Christ1 and G: brhtrup.

123

I..Mehrotrsi

and-D..Devaprabhaks&J:-&g&omet&l.Chem.,

124

H:Hogeveen

and B.~J.~NusSe,~Tetrahedron-Letters

225

G.

126

D_B.‘Ledlie, J. Knetzer and A. Gitterman; J.Org-Chem.;.39(1974)

127

A.E. Hill and H.M.R. Hoffmann, J.Amer.Chem-Sot.,

128

f.

129

CD.

130

B.Gan.em and R-K. Boeckman Jr. Tetrahedron Letters,

131

M- Hajek, P. Silhavy and J. Malek, Tetrahedron-Letters,

132

-D-N- Kevill and C-R. Degenhardt, Chem. Couunun.,

133

R-

134

T_'Tatsuoka and Y.Sugihara; Tetrahedron Letters,

Schmid

and

H-

S&mid.

Helv.Chim_Acta,

L-V.

C.A.

Sl(l974)

Kostikin

and

V-A.

(1974) 3193. 662.

1883.

96(1974) 2654.

136

L-I-

Ginsburg,

(1974) 178.

Zh.Org.Khim_.

lO(1974)

1327561~.

Ito, Y. Inubushi and T. Saegusa, Tetrahedron Letters,

137

y-

138

A-N. Nesmeyanov, E.G. Perevalova, K-1. Izv.Akad.Nauk SSSR,

(1974) 199.

(1974) 917.

(1974)

57(1974)

Reich and H.J. Reich, J.Amer.Chem.Soc.,

Sankina,

708.

39(1974) 3875.

c- Georgoulis and J-M- Valery, Bull-Soc_Chim.Fr_

S&.Khim.(l974)

(1974) 1283.

Grandberg and D.A. Lomenovskii,

1124.

C.A.

Sl(1974)

49718b.

A.N. Nesmeyanov, K-1. Grandberg, V.P. Dyadchenko. D-A. Lemenovskii and E.G. Perevalova, Izv.Akad.Nauk SSSR., Ser.Khim.

140

..

Y6(1974) 4597.~

135

139

Cf.‘..

82(1974j

and L. Faquette, J-Amer.Chem.So.o.. Y6(1974).-5478.

Beard and K. Baum, J.Org.Chem.,

460.

.. ..--:

:

-(1974) 159.

.:

Murata,

.1-L-

:.

j

-J.Amer.Cheis.Soc-, 96(1974) 7454.' _

James and.G-H. Binberg,

122

Zen

._. : : .: :‘.: f .:_;;. ..:.

E.T.‘Blues, D-Bryce-Smith,

(1974) 1206.

I.W. -Lawston and G.D. Wall, Chem.Commun.,

(1974) 513. 141

P. Braunstein and R-J-H. Clark, Inorg.Chem., 13(1974),2224.

142

V-I. Sokolov, K-1. Granberg, V-V. Bashilov. D.A.- Lemenovskii. P.V. Petrovskii and 0-A. Reutov, Dokl.Aked.Nauk

SSSR, 214(1974) 393.

143 -G. Van Koten snd J.G. Noltes. J-Organometal-Chem..

C.A. 80(1974) 96117u.

82(1974) C53.

: : ..

_.

._.

.,

_. .. ..

: ..._

.

: ..

-144

459.

-.

..-A/N_ Nesmeyanov; _,:

E.G.

T.V.

Perevalova,,

Baukova

and

K-1:Grandberg,

Kosina,

Izv.Akad.Nauk

Izv..

_. .-:I

Akad_Nauk.SSSR,--Ser_Khim_, I45 1

Khim._ (1973) 146

E-1.

K.-I. 'Grandberg,

A.N.

&.Akad.Nauk 147

A-N.

Baukova 148

V.G.

150

K.C.

Afanasova,

0-B. (1974)

Afanasova C.A.

484.

K-1.

and

and

Grandberg,

E.R.

K-1.

SO(1974)

Grandberg, 49774s.

D. Lemenovskii,.T.V-

J.Organometal.Chem.,

Struchkov

Ser.

83173j.

Perevalova,

R. Hiittel,

J. Eberlein

65(1974)

Rossinskaya,

131.

Zh.

Strukt.

Khim.,

Chem.

and

H.

Ber.,

107(1974)

Schmidbaur,

3761.

Syn.Inorg.

Metal-Org.Chem.

375.

P.W.J.

De Graaf.

C&em.,

iS(1974)

J.

153

A. Tamaki,

154

R. Uson,

155 A. Tamaki

Boersma

S.A.

and

J-K_

A. Laguna,

Kochi,

P. Dixneuf

and

M.F.

J.E.

159

G. Minghetti

and,F.

160

G. Minghetti

and

161

D.I.

Hall,

162

B.B.

Wayland

163

D.A.

Couch,

S.D.

Robinson

and

164

G.P.

Fenske

Jr.,

and

Mason,

W.P.

and

Fehlhammer,

A.L.

J.H. and

Balch,

J.Organometal.

V.K.

and

Sutcliffe,

Chem.,

J.

JCS

Dalton

R.S.

Nyholm,

J.N.

(1974)

71(1974)

73(1974)

13(1974)

Wingfield,

Inorg.Chem.,

JCS

361.

1827. 13(1974)599.

453.

1600.

Struct.Bonding

Inorg.Chem.,

6140.

411.

Ed.Engl.

13(1974)

J.Organometal.Chem.

96(1974)

69(1973)

64(1974)

Angew.Chem.Intern.

Kapur,

W.R.

Lappert,

Inorg.Chem.,

F_Bonati,

L.H.

J.Amer.Chem.Soc.,

J.Organometal.Chem.,

Bonati,

Ling

Kochi,

J_Organometal_Chem_,

158

Parks

Kerk,

and

J.Organometal.

K.

and

der

Puddephatt

3-K.

and

157

Bartel

Van

c21.

69(1974)

Magennis

P. Royo

Cetinkaya,

G.J.M.

R.J.

A. Johnson,

Chem..

and

and

ClY.

Hargreaves,

Organometal.

156 B.

Ser.Khim.,

Yu.T.

and

Dash,

3<1973)

N.G.

SO(l974)

SSSR.

74.

P. Tauchner

152

O.B.

A.N.

Perevalova,

E.G.

Andrianov,

149

151

SSSR,

and

lS(1974)

C-A.

E.G.

Nesmeyanov,

866.

Smislova.and

2787.

Nesmeyanov,

(1974)

C43.

(Berlin),

15(1973)

2517. Dalton

13(1974)

(1974) .1309. 1783.

3.

-. ._- ..: .., : .:-:.._ . .. . ._ _ ~_ I ..;norg.Chi~;Acta,. 9(I974) 39.: 165 D.A. -Couch and.S;D,':Robinson; _/?., 456!.. 166 D.A:[email protected] S.D. Rob~nso~;-;I~~rg,~~m;~;~-i3(197~)~ -..

460

:

.-.._

.,

._.. ._: -..-. ::.-: -.'.._ : ‘_: :: ; : ._:.‘.--. _.

167

Ii. Levason

168

R.J.

Goodfellow

169

A.G.

Jones

170

P-L.

Goggin

171

A.G.

Jones

172

F. Calderazzo and D. Belli Dell'Am
173

G.

174

A,N.

Nesmeyanov,

K-1.

Grandberg,

and C-A.-McAuliffe;_Inorg.Chim.Acta, and

and

D-B.

and Jand

Rainoni

B-F.-.Taylor, Powell, Mink,

D-B.

and

A.D.

JCSDalt&(1974)

..

3UA(197.4)

563.

’

Dalton-(1974).:1479. Spectroc-him.Act$A,

Zuberbuehler,

E.G.

25.

1676. . .

Spectrochim.Acta,A,-

JCS

Powell,

8(1974)

Chimia,

Perevalova.

Izv.Akad.Nauk.

D-A: SSSR,

30A
28(1974)-67.

Lemenovskii,

C.A. V.P.

Ser,Khim..(l974)

80(1974)

Dyadchenko

1661.

C.A.

125341~. and

81(1974)

105642m. 175

A-N.

Nesmeyanov,

K.I.

Grandberg,

E.G. Perevalova.

Izv.

Akad.Nauk

C.A.

81(1974)

Division)

13618e.

23(1974)

See

V.P. SSSR,

also

Dyadchenko,

D.A.

Ser.Khim.

Bull.

(1974)

Academy

Sci.

Lemenovskii 740

USSR

and

and

1661.

(Chemical

Science

1587.

176

K.W.

Muir,

177

N.C.

Baenziger,

178

A.P. Gaughan Jr., 2. Dori and J-A. Ibers, Inorg. Chem., 13(1974) 1657.

179

D. Coucouvanis, N-C. Baenziger and S.M.

180 G. Nardin 181

R.D.

Mol.Struct. K.H.

and L.

Willet

182 M. Textor,

and

Diffr.Methods, Dittemore

Kandaccio, C. Chow,

E. Dubler

and

and

Acta

l(l973) J.R.

631.

Doyle, Tnorg.Chem., 13(1974) 805.

Johnson,

Cryst..B,

Inorg.Chem.,

30(1974)

Acta

Cryst.,

B, 30(1974)

H.R.

Oswald,

Inorg.Chem.,

207. 13(1974)

and

K-L.

Kalra.

Inorg.Chem..

13(1974)

1065..

184 M.R.

Churchill

and

K.L.

Kalra.

Inorg.Chem..

13(1974)

1427.

M-R.

Churchill

and

K.L.

Kalra,

Inorg-Chem..

13(1974)

1899:

186 R.C..Larock, Intra-Sci.Chem.Rep.7(1973) 95. 187 D.G.

Holah,

A.N.

188 J-C.

Bommer

and

Hughes'; K-W_

C.B.

Morse,

Hui

and

K-Wright,

J.Amer.Chem.Soc;.

1191.

1377,

183 M-R/Churchill

185

13(1974)

1361.

..

C.A. 80(1974) 9606Ov. Canad.J.Chem. 96(1974)

6222.

52(1974)

..

2990.

461

189 K-M. Melmed,.T.I. Li, J.J. Mayerle and S.J.Lippard, J.Amer.Ch&m.Soc.. $6(1974) 69. 190

.T.E. Paxson, M.k.

Hawthorne; L.D. Brown and W.N. Lipscomb, Inorg.Chem.,

13(1974) 2772. .191 C-S. Arcus, J.L. Wilkinson, C.Mealli, T.J. Marks and J-A. Ibers, J.Amer. Chem.Soc., 96(1974) 7564.