.. 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.