Nickel, palladium and platinum

431

NICKEL,

PALLADIDM

Ah%UAJ_.SURVJZ

AND PLATINUM

COV!ZRING'!ZiJZYEAR1975

D. M. Roundhill Department

of Chemistry

Washington Pullman.

State

University

Ctashington

99163

co?rENTs

I. II.

III. IV.

Netal-carbon Metal Metal

432

J complexes

complexes

formed

by insertion

and r&aced

reactions

carbenes

Internal

metallation

V.

Metal

carbonylS

443 447 450

reactions

452

and thiocarbonyls

VI.

Metal

olefins

455

VII.

Metal

acetylenes

463

VIII.

Metal

allyls

468

IX.

Delocalized

carbocyclic

473

systems

X.

Metal

hydrides

475

XI.

Metal

carboranes

477

XII.

Metal

isocyanides

XIII. XIV.

Catalytic Complexes

reactions

479 involving

and reactions

481

complexes

of gereral

484

interest

ABBREVIATIONS

DPH

his-1,2(diphenylphosphino)methane

DPE

his-1,2(diphenylphosphino)ethane

DPP

bis-1,2(diphenylphosphino)propane

DPB

bia-1,2

en

ethylenediamine

acac

Pn

propylenediamine

THF

tetrahydrofuran

bipy phen

2,2-bipyridyl

1,5-GOD

1,5-cyclooctadiene

l,lO-ph-throline

i=

1,2-pyrazine

PY

PyrMhe

Iickel. Palladio3Land Platinum, Annual Survey covering tal;Chem., .s&eJ..Organome 123 .(1976) 303-423.

the year 1974

.

432 1.

Metal-carbona cmplexeS A number of metal alk,.ls have been prepared by oxidativeaddition.

TreatingPtt4(PPh3,A&h,,) rith g-XCl$C6HLCN(X - CI, Br) yields transUganda L can be displaced

PtX(CH2C6H4CN)L2[l]. ligande,

L

and facile

CH2C,H4CN

‘Ft’

2:’

‘L

insertion

of CO into

the

by bidentc
R-C

phosphorus The ttans

+AgBF4)

c+%C6H4CN

L

/\‘Pt’ x L complex is thermodynamically by free L occurs

the stable

in C?12C12solvent.

XRCN(X = Cl.

Br; R = (CH2),.

AsPhj) yields

cis-

and/or

that alkylatioo

have been prepared -Cl.

43,

but cis-trans

isomerizarion

the oxidative

addition

3) to PtL4

trans-PtX(RCN)L2[2).

U

Isolation

on the platinum

by the oxidative

of

center.

addition

of

= PPh3, PMePh2.

The reaction

PtI(Ph) We2 CL) f 31.

PtMe212(L)SMe2.

occurs

Similarly

n = 1, 2,

i :SMe)PhL12 IL = PEbeZPh) gives [Pd%e)MeL12 gives

isomer

of Me1 with

Similarly

[Pt(SMe)Me21(L)]2 Arylnickel(II)

verifies

compounds

RC,.,H&X (R p H. m_of g-Me,

of

and OPh, j+Me, -CO&, and CDPh, and m-CO Me; X = Cl, Br, I) to -

2

NW~3)v. _. A linear correlation of rates against Wtt’s tith u > 0.23 for elmttm vithdrw aubstltuents i4].

d is

found

Bcntylaickel(11)

434 Benxenethiol reacts with -cis-PtMe2L2 (L = PMe3. to give CH6 and trans-PtMe(SPh)Ll or trans-Pt(SPh)lLB.

PMe2Ph,

reactions. P~h3)

t PhSH -t trans-PtMe(SPh)(PMe2Ph)2

-cis-PtHe2
for ButMeN

have also carried

platinum(II) ating

in the presence

for a contribution

power

Complexes

bands

out a similar

by haride.

for several

by treating

riate Grignard bromotoluene

with MeLi

aryInickel(LI) -elimination

[161-

A procedure The Grignard

been used

aryl

has been

complexes

c191-

The halide

yield

the cationic

PMePh+

PtMe3

or lithio

followed

with

(L = PPh3, mixed

of 80%. has been reported

followed

by anion

replacement.

has

(M = Pd. X = Cl. Br. I,

[I&l]. This method

was extended

Maloarylnickel

region acids

the dimers

by 3.5-lutidine

to

such as AIEtC12

for propylene

into monomers

[22)_

yields Addition

PdCl
by treating

.F5G6/.‘cd .(2)-

:

~.

In

the complexes

show

than do NiCll
betveen

compounds

of further Complexes

‘L

m_

has been

PdC12L2

binuclear.compounds

PdCl(x-CjH5)PPhj.

L\d/c1\pd/c6F5

c-tolyl,

The reaction

and AlEt2Cl

of the reaction

and T1Br
have been

phenyl,

spectrrrm [211.

dimerixation

to

(L = PMe2Ph.

complexes

for aryls:-

of the electronic

compounds

prepared

bgpyridyl

and X = I, Br, Cl.

A reexamination AsPh3)

complexes

[Ni(C6C15)L3_n(3.5-lut)nJC104

and aryl halides

activity

PPh2Me,

have been

and by aryl bromides

in these

compounds

with mononuclear

converts phevl

methyl-

the reductive

can be replaced

Lewis

and NiEt2(bipy).

and o-

Intermediate

by oxygen

MX(C6Cl,)(PPh3)2

or g-chlorophenyl

catalytic

the approp-

(X = Cl, Br. 1, NCS, NCO. N3, CN, NO,)

in the visible

combination higher

with

NiX(C6C15)(DPE)

from Et2Ni(bipy)

tolyl, ptolyl

[l&l_

of bromobenzene

and interestingly

in yields

method,

complexes

n = 1. 2. 3) 1201.

prepared

of methyl-

+ MeLi + NiMe(Ar)(PEt3)2LArMe-

NCO, NCS, N3; H = Ni. X = NCS. NCO. N3) prepare

of methyl-

developed

chlorides

studied.

is accelerated

to prepare

to prepare

as

These

the gradation

has been

coupling

have been prepared

NiBr(Ar)(PEt3)2

[171-

showing

nickel

The cross

and MeMgBr

of alkylated

[13]-

(X = F. Cl, Br. Me; R = Et, Bu) have been

1151.

complexes

presented

pathway

on the cleavage

complexes

the correspording

reagent

+ CM4

has been

chain

study

A series

methylmetal

(~-xc~H~cH~)~N~~PR~:R

prepared

of BhNO

fron a radical

PMePh2,

Observation

ligand of

(2) L

tetrachloro-

PdCl(r-C3B5)pp

and PtCl(n-C3H5)PFhg

with

by C&K14

compound

1231.

The

c&-PtMe2(PEt3)2 reported.

with

CP3I

complexes

appears

(acetylacetonato)

the

phere

presence of

a slight

A number

of

ring for

the

of

Thus

dione.

activation

first

[25].

the

is

replaced by treating

tu prepare

is

aryl-

The reactivity

+ SnClMe

of

3

+ SnClMe3

sequence

Pb : Sn

NlPh(acac)L

from

at

Ge .* Si.

(L = PCy3,

Nilacac),

phosphine

and alkyl

PPh3)

and A1Phg*Et20

-20°C

under

an atmos-

transfer

opening

of

the

with

I being

_ kinetics

in

for

CHC13 is

127).

r

is

the

zero,

presented

are

the

zerovalent

platinum

step

Interestingly

preferred

have

been

platinum

and Pt(PhCZCPh)(PPh3)2 in

rate-determlnlng

entropy

reactions

benzocyclobutene-1,2-dione,

4-methoxy-3-ohenylcyclobutene-1,2-diane,

order

Two schemes

positive. scheme

halide obtained

19F nmr data

used

complexes

Pt(w-PhCH:CHPh)(PPh3), follows

diphenylacetyleneA the

in

3,d-d~methoxyc~clo~uttnc-l,2-dlwIri

reaction

[24].

been

prepared

ring

3-phenylcyclobutene-l,Z-dione,

in

3

excess

opening

Kinetics

complexes

is

+ PtArRr’(COD)

nickel(II) been

the

N2 [26].

reported.

a%

25°C

conditions

ta decrease

have

of

mild

+ SnAr’Ne

and NiPh(acac)(PEt3)2 in

at

have

+ SnArMe3 + PtClAr(COD)

PtClAr(COD)

Phenyl

48 hr

reagents under

PtCl2(COD)

IV compounds

HC141 jTl.vhen o e-PtI(CF,,)(PEt3)2

for

Aryltrimethyltin

platinum(II)

Group

(2,3,5,6-’

to

but

of

opening in

this

methyl

stilbene

it

latter transfer

Is

between

0

e[Pt(PPh3)2]

(Ph3P’2pt

f

phwO

I +-QI

0

0 SCHEME 1

Ph

sm

2 (i),

-PPh5;

(ii).

or

+ PPh3

;tep

markedly

effect,

1 Ph

order

isomerizacfon

benzene

explain

the

and zero

dissociation

ring

Hononuclear

show

complex

with

436 ad

beteronuclear Reaction

1281.

-cis-P~(N03)(pMe2ph)2

ptMe2(coD)

which

trans

isomer

tion.

A number

-

of threo-

of vinyl

structures

palladium
with

and ylide

and Pt(I1)

transfer

proceeds

LiqlD4

compounds with

of two addition

Sdiketonate

slow

isomerization

l

PtC12(COD)

Pdcm(PhW2 + PdCl.Me(PhCN)2

from threo-

with

to

retention

and erythroof configura-

rings:

to

[301.

have

ligands

products

been reported.

Complexes

Ph2P(CAZ)*~(Phl)~C(0)R

(n = 1, R = Ph; n = 2, R = Me, OMe) have been crystal

is facile yields

and erythro-MeCH(NHe2)CH(He)PdC1(PhCN)2

can be effected

of the chloro-Pd
and pdlladium

‘PtClXeKOD)

2o"c

Alkyl

to palladium
Degradation

subsequent

Ooc

[29].

platinum

and cis-Pt(N03)2(PKe2Ph)2

undergoes

+ PdCl,(PhCN)2

E4eCH
the free amine

between

+ Pdci2(Phm)2

PtClMe(COD)

the more stable

transfer

methyl

of cis-PtMe2(PMe2Ph)2

prepared

(3) [31].

of hexafluorobut-2-yne

The with

cis-bis[l.L-bis
acetyl-4-oxopent-1-enyl-O,Cl] palladim(I1) and -ab-[1.2-bis(trifluoromerhyl)-3-acetyl-4-oxopent-l-enyl-O,Cl~-~d-~2-~d~e~hyl~ino)~thyl] -

PdC12(PhCN)2 TliF



PdCl,@hCN)2

LiAlD4

TEF (erythro)

(erthyro)

437 phenyl-Cl.Nj

palladimn(II)(44)(5)

rearrangement

are reported

intermediacy

of a pentacoordinate

\

coordinating

L

is favored

by

PdJo=C(M-C(0)We \c=/-

'CP

CFf

3

solvents-

PtX(CF=CF2)(PMePh2)2

'CF

The reaction

72 \

I

3

has been

and PtX(CF=CF2)(PPh3)2

(Ph2KeP)2Pt

of the vinyl

indicates

Ne

cEc/

CP' 3

A study

TIE reaction

species.

Meko M&(0)-U/

C321-

and Pt(C2F3Br)(PPh3)2

of Pt(C2F3Br)(PMePh2)2

used to prepare

complexes

(X = SCN, N02, NO?, OAc)

1331.

I _I F

+L-

(pb2~p)2~~Cp2

CFBZ

(

;r

1 Ph2EifZP

cF:cl?*

'R' Br/

Anionic

2

phenylpalladirnn
type [B*R3P]2[Pd(CH)2] spectra

\PMePh

are reported

-

complexes

are allowed and discussed.

5~[Pd(CI?)2].~

to wan

are formed when above

Complexes

+ iIKN i. 4[R'R,PlX

-4O'C

compounds

1341.

L12[Ni(C2Ph)4].4THP.

-34%

of

Infrared

438 LiZ[NiPh4]_4TNP, = anion

and Lit[N~4]_2THF

are obtained

of 1,3-bia(2-pyridoylimino)isoindole)

at -7B°C

[35]_

The crystal

structure

at Pt and P which

are approximately

P-Pt-P

and Pt-P-C

1361.

distortion

angles

low Pt-P

of these valence

- . .._.

The angles

coupling angles

15" less

shows

Ni
LiPh,


or LiMe

internal

ring

than the unconstrained

are normal

constant

and it is suggested

is a consequence

in the 4-membered

HC4)

LiC2Ph.

of Pt
angles

char the unusually

by treating

with

of the

ring.

CCZI I

: .

. -.

. -.: ..

439 A series crystal geometry carbon bent

of metal

structure about

atom.

having

keto

groups

The benzylacetoacetate

Pd.

The acetoacetate

perpendicular

is again

alkyls

of PdC1(CHH,COCH2COOCH2Ph)(py)2

moiety

bent with

its phenyl

1371.

A coupling

constant

is coordinated

planar

by the terminal liqand

and the terminal

plane,

ring approximately

The

reported.

has a square

in the benzylacetoacetate

to the coordination

tion plane

have been

parallel

is

benzyl

group

to the coordina-

Compound

(6) has been obtained by the route shown 195 Pt and the methine proton, of 113 Hz betveen

[38]. in

)pCCl* one

Ph

As2

-

C=CH H 2

addition

to the observation

protons,

is presented

A detailed

analysis

of a temperature

as evidence

dependence

for the formation

of the infrared

spectra

of the methylene

of the Smembered

of complexes

(7) and

VO, Co, Ni, Cu. Zn, Pd for n = 2 and M = Fe for n = 3) has been t391.

Assignments

have

been assisted

by using

The C 0 groups

retain

second

For the allyloxycarbonyl-

metal.

the keto character

isotopic

even after

metal

ring.

(8) (M = performed

substitution.

coordination

of the

and N-allylcarbamoylplatinum(II) 1--------I

1

4

K+

,!3;Jt. --,

CH3 _%

H H3 (7)

complexes

(8)

Pt(COXCHR1CR2=CHR3)C1L2

-PPh2Me. PPh3) CzC bond

[40].

treatment

with

there

The compounds an equimolar

undergo amount

PttcOOCR*CR2~*)clL2+

-?osaible

mechanistik

(X = 0, NH; R1, R2, R3 = H,Me;

is no significant

pathways

PtCl(CF2COCP2Cl)(PPh3)2 [411:. &l:Si. n&r study

shows

interaction quite

facile

L=

platinum

decarboxylation

and the upon

of AgC104.

Agc104

-Agc=w

are discussed. a very

l"Pt-. ,/

*>R2

The crystal

long Pt-P bond

of the trimethylplatinum
Lineti~=.rlgidldislera.are-present

between

in solution.

tram

Cl04 + co

structure

2

of

to -CF2COCF2C1

compound

<7) show

The I:1 adducts

with

that py

440 a&d bipy have been prepared I&2]. the b

nmr of the

acetyLacetonste

compound (7)

ligand

is

first

A

quantitarive

analysis,

(R = Me) haQ shown that order

and proceeds

how@v@r, of

exchange

predominantly

of

the

by dimer

E(

12

R2 * axe: Rl * u2 - mt:

RI* dtiscckzti~

tit@

tu@ separatedpenracaordieatea specieat The actiWt~Cm

energy 1s 6l.S + 0.8 W moImL 1431. The auk& compleaeepent-thy1 (8) and h-thy1 (9) p&ttiate(EV) bava beeu prep&fedfrm (PtIB%3),and &-

441

P~4
vith

methyllithium

of complexes

R = H, Me, Pri, CH2Ph.


Ph have been

12LiMe

-

and %I nmr spectra

1441. The infrared

PtMe,(~-OC6X4CI-I=XR)X

with

studied

4Li2(PtHe6)

X = lutidine.- PPh3,

of

and

1451.

f 4LiI

8LiMe

PPh3 I

4Li[PtKe5(PPh3)]

+ 4LiI s

4Li2(PtHe6) (9)

(8) LiNe _PMePh2-

cis-PtMe4(PMePh2)2

Pm,

decomposition

Bun, Bus, PhCH2,

MejSiCH2)

has been

studied having

solvents

tion occurs

by a B-elimination

> PhCH2

not involved. the presence elimination

The pyrolysis

reaction

PtPh2
the cyclopropane Depending propane

1471.

+ DPE

moiety

on the new ligand

cyclopropane

because

has been made

4800KD

Pt
are given.

reacting

displaced-

with

A speculative

,-_L

X

&L) +H

-

by

of the reductive of

(X = Cl, Br; L = THF, py, en). the system.

mechanistic

either

L or cyclo-

for the evolution

scheme

is suggested

of C481.


=\P

I0 k

+

J

23

ut ..

+

are

is facilitated

+ Ph2

? (CL2) 0

is

pathvays

of the displacement

Rate law plots

f =\P L/I

Radical

complexes

A study

decomposi-

of stability

of the promotion

from PtX2(C3H6)L2

is preferentially

a &hydrogen,

> Bus Q Bui.

of diarylplatinum

ligands

(R = Me, Et, Pri,

by ItI nmr spectroscopy

The order

reaction.

> He > Et % Bun =- Pm

of added

r-cpNi(PPh3)R

For compounds

in aromatic

Ke3SiCH2

-PMePh2 I Li2(PtHe6)

of complexes

1461.

1

Li[PtHe5(PMePh2) Li&

Thermal

+ 4PPh3

X

mm -

L\Pt

[

(>

n/l X

I

x-

(HCL)'

442 r

L

L\b

7+

.

I 1

(McL)*+L-

x-

(MCL2)'

M/1 u X

-h L\[t

(MCL). •i-He

x- (M2CL) *

3 M'i X -[

.

(NCL)' i- s

m

w2cL>=

I

cyclopropane

M-t-L+

x-
M

(MC) ’

-

I

I

\Pt

-M2PtX2

+ CH2CH2CH2

3

r/I X Further &-tz

work

Ph, =-HeC6H4_ made uith

E-EtC6H4,

the rates

[PtBr2!3e2ln with which

has been carried

isomeriaation

converts

undergo

of square

2,4,6-MeVC6H2,

for halide

aqueous

of reactions

of salicylaldiminate

factors

complexes

E-MeC6H4.

substitution

E-FC6H4)[49].

yields

upon neutralization. with

halides,

or 6-thiodiketonstes

lutidine.

[SO].

involved

in the

PtBr(Ar')(PEtB)2(Ar'

by MeOH

AE+ in acid solution

to [PtBr
a variety

out to deduce planar

Comparison

= is

Treating

[PtBrMe2(H20)31f. These

compounds

and nickel

The enthalpies

complexes

of the

443 of

reaction shows

a Series

3 good

enthalpies

of

Group

cutrelntlon

with

from 27.8

ing ta a change

in

to 0.5 cone

Alkyl-

prepared

the

hy treating

Analogous PtMe2(phen) spectra

in

the

n-bonding

in

It-Fh

(PtMeL(C011)]PF6

three

a neutral llgand. 1 2.J .Jptl(COD) PtnaC v4 : been uh~d to determine

Metal

has

been

cis

llgand

chelate.

The abservatior complex

in a square-planar

hydro

CO, PEt

and

of

that

olefin

of

13C

placlnum,

anionic,

‘C(TOD)

and

and hai; also

into

into

complex

alkones

of

rannot

contains

ethylene

adopt

complexes

a Pt-H

bond

a

and cannot

insertion

to

occurs

become form

even

mutuallv

an

cis-orlcnta(L

and tm-F’tHX(PEt3)z

+ C,\$

a

in

transd[PtHL(PEt3),]PF6 -I_-

ttans-[PtH&H4)t2]+ I-*

(Lf

of

the

reactians

posttionq.

P(OPhjj)

Pmlc)j,

vs

ethylene

insertion

For

of

are

incorporatlon

and related _____--__

ethylene

ligands

complex. ASP113.

J’

facile

shows

,

[5&l.

tram

the

made of

complexes

5C(TH3)

deuterium

L&IV

he suggestive*

been

l3 C nmt spectroscopy

insertion

spans

been

The electronic

R and R’

The hydroplatinum(lI)

which

when the

I,54230 where

complexes

the

of correspond-

WI rn ,.--,)11+“r

to

has

of

b_y insertion ___---1 of

[ 551.

tions

study

[53j. of

reported

[52].

are considered

correlations

poslclon

The range

compounds

prepared

T-bonded

plltlnumlI1)

case5

acetone,

the

(P = P?le2Ph)

[Me2PCH,CH,PMe, to _L I complexes have

1,5-COD

and PtRR’(COD)

report

ethylplatinum

f

of

the

(10)

190”

been

region

formed -_

,iublSshed

hidentate

to

have

Linear

complexes

An interesting

107”

.zre presented

phosphlne

L 1511. -1 are

lhol

A svstematrc

series

L is

[PtMe(THF)P2]PF6

and aryl-(bipy)Pt(lI)

bond.

of

Il.

of

charge-transfer

the

cone

appropriate

PtMeR(COD),

tertiary

angle

complexes

nmr spectra

and

with

the

for -:\H in Kcal

angle

P(O-+6H3(Me2))31.

V donors

(X =

+ iPtH(C,H;jZLZ]+ (5) I

a-[PtEt

Cl, N03. NO29 CN) the facility follows

the

> Cl 7 NO2’

order: CN,

of the insertion

to

L = acetone PhCCMe

inserts

of RlCrCR2

the

elk&y1

group

geometry

has

been

of

olefins

more

readily

than

PtHX(PEt3)2

shown to

be cis

vithdrauing

solvent

for cationic

substitueate

and

[56].

X = NO3

In a stud<

Cl,

acetone,

MeOH)

Pt and R. The formation

about

but ia favored

on the acetylene

complexes and a non-planar

PEta;

Rl = Ph. R2 * Ph,

(X * NOj,

about Pt ie sot always observed

electron

Cpltlr

C02Me;

+ CZH4

and acetylenes

‘l> CO 5 AsPb3 b P(OPhj3,

(R, -Me, R2 = Ph.

CP3; RI * CO2He, R2 = C02Me) into

of a cis

insertion

IS)L,]+

(ii)

solvent

by Ii)

a coordinating for neutral

ComPlexI

444 (iii) the presence

of a more

strongly

coordinating

(R = Et, Ph; L = tert. phosphine,

PtMe(R2gpr2)L acetylene

complexes

CP3CPCCE3

the methylvinyl

vith

PhCPCPh

anion

and PhCZC:CHe
compounds

X [57].

isocyanide)

are obtained

form

Complexes stable

With HeO2CCZCCO2Me

[58].

and

In a continuing

(11)

study of the reactions

of dimethyl

chloride

of {[chloro(methoxycarbonyl)(1,2.3.4.5-penta-

the structure

acetylenedicarboxylate

with

Palladiua(II)

ki~ethoxycarbonylcyclopenta-2,4~ienyl)-2-~OCO]methyl~~acetylacetonate~Pd~~~~ has been reported bridged

dimer.

(12) 1591.

and products

This compound obtained

CN-, sr-, HCl are also described.

is formed

from treating of

The insertion

from the chloro-

this dimer with dimethyl

PPh3.

a_cetylenedi-

carboxylate

(12) into the Pd-C bond of trans-PdCl
P

<13)t601.

Treating

PEt3 CO2Xe

Et3

Cl-Pd-CECPh I

PEt3

yields

+

&~o~cc-~~I&

:

+

trans-PdCLT_C
PdC12 with He02C~~2

I

I

-

tSe in IfeOH

445 yields

(PdC1~HC8(C02Me)B]12 vhich gives PdCl.py2[iK8(C02He)8] (14) with A single

pyridine. Pd(IX)

tion

complex

[61],

structure

Ni(allyl)2

nickel&e

effects

from the deuterolytic intermediate

Diels-Alder

reactions

CFJCxCCP3yields

(15) and (16). Addition

the Pt atom substituent

no rrcral

participation

prtcourdinrtion (17)

of the

[63].

via

aham

The formatian the author9

c&-diallyle-

of

1,4-

to postdlatc

a

that

part

crystal

structure

of

of C4F6 to the ring on the as implic&,ion

or activation

c4P6 wlecule.

of

and Pt(n’-C5Ng)#OD A single

la presented

a tcatplate

attacking

af 7,f,IJ,8-ttrr~c]ruui~~~th~t

Pt(CBClb)2(Pkleg)2

to be a Scoordinatc

the stereoapcclflc

of PtMe(n’-C5H5)COD

adducts

side

opposite

shows it

[62].

has been solved

&duct

(14)

vorkup leads

compound (15)

k

of

of PhCECPhand PhCWMe in X&50% yield.

d2alkadiene

vith

crystal

aechaniam

A crystal

that

there

arid no

structure

of

the

(‘L’CSQ)to crmathe TCrtQis bonded to tha a-carbon.

446. and the other

philic

parr

olefins

to the g-carbon

such as l,l-dicyano-olefins

= Pd, Pt.) [651.

%f nmr evidence

compounds

The Pt compounds

(18).

ofl,OO°Cor

cemperanmes

tended

to be unstable An ionic

CE3CO2R.

at room

C(_)-CR2R3(I.)n isocyanides

undergo

has been

bond of complexes

facile

reported

The insertion

a new compound

only

are cleaved

“\t/

to

into the Pd-N

Aaido

bridged

X

(Ph3P'2?102

+

,7

I”-?/

(Ph P) M 3 2'c'\2 -

Y

PY

N = Pd or Pt

R1 = R2 rxzy=cpq X

=Y

X

= Y = CN, R1 = El. R2 = C6HS

X

= Y = CN,

X

= Y = CR. R1 = 8, R2 = p-N02C6E4

X

= CN. Y = Nfl2, R' = H, R*

X

= CN, Y = NO

X

= CK

X

'_H. Y=ND

X

p.Y.=

= R2 = CR3

C&R1

R1 = H, R2 = ~-CH30C6R4

Y=No

Cl?3' Cl

2'

R'=

,;$.=

* V5

Ii, R2 = E, R2 =

R1 = R2.s CR 2' -3 RIL

R2 *-R.

E-CR3c6E4 E-Ch3CC6H4

with

of these

of type kl-

groups

of CyNC

(20) [671.

at

Pd complexes

complexes

methylene

(M

of the

for the formation

of active

1661.

decomposition

The complexes

of C-monohapto-vinyl

(19) gives

F102(PPh3)2

for the structures

is proposed

from the additfon

Electro-

[64]_

the corresponding

temperature.

type mechanism

ligand

add to complexes

is presented

whereas

higher,

The preparation

compounds-

of the Propynyl

447 = H. R2 = C6ii5

X

=Y=COCH3,R1

X

=Y=C02Et,R1=R2=CH3

X

=CN.Y=C02Et,R1=R2=CH3

o-o (Ph 3 Pl$i’

*c /\ X-

[M(CNMe)412+

i- 25H +

+ 2H2C(R)CN

(MeNC)2M c

complexes bridged

[MR3(dieneOPle)]2

compounds,

form thiatriaaolate

cyN3z

CS2, CF3CN and SCNPh

or tetraaolate

groups

?’ \ R’ .Y

+ 2H20

CO to form the cyanato-

by 1,3-cycloaddition

as bridges

1681.

Cl 'Pd/ / 'Cl

complexes

CyNC,

have been

of C2H4,

C3H6 and l-C&H8

Nli3, PhCR2NR2

* 2

formed by insertion

from nucleophilic

acylpalladium(I1)

H20

-SiMe

obtained

attack [691.

complexes

of CO into the a-alkyl

of Et2NH

A similar

on the Pd(I1) approach

from carbonylation

and phthalimide

carbomethoxylation

on PdC12(COD)

of a-bonded

mercurials

A study

in the presence

III.

Metal

carbene

Cationlc the nickel

of perchloric

F X-NiNRUi :.

acid

predominant

of configurathat

retentions.

of nickel(I1)

(22) have been prepared

(2l) with ROE in the presence 1721.

Subsequent

L Rem

HC104

addition

he

by treating

of an equivalent

of base yields

Cl04

amount

a further

Et3N_

OR

x-L-c/

by

of stoichiometric

complexes

carbenes

acetylide

with

of

of attack

of the

of 7.52 PdCl 4 and CO proceeds with predominant retention This leads the authors to the conclusion tion at carbon [71]. of Pd for Hg occurs

complexes

has led to isolation

of the products

[70].

compounds

chloride

amounts

exchange

to

Acylpalladium(II)

SiMe3

/

Ph3P-N

R

(H = Pd, Pt) react vith

and with

-/

1

-C<;z

(M = Pd. PC; R = CN, C02?fe)

R’

lEic1o4 _--_

449 and imidazoles

pyrroles.

have

[PtC1(CNCH2C02Et)(PPh3)]BFq 13C nmr study

of carbene

from comparisons

carbene

13C shieldings,

carbene

and the aromatic

respect

shift

to the carbene

of substituted

chemical

implications

coupling

of a cis methyl

aminolysis

those

of methyl

Pt(I1)

reaction

The reaction

constant

Treating

ethers. terminal vinylic

acetylenes

the hydro

alkoxycarbene

complexes

compounds

to carbene

complexes

Platinum

of a product

carbene

complexes complexes

t R OH ~

+ HCZCR

bond,

infrared

complexes

are reported

I

[83].

of these

In a study

than

(31) or alkylation of an isocyanide

cationic

secondary

of the thermolysis

(32) at

into a Pt-Ii carbene of complexes

(31)

=2s04 !?aClO,-

(30) rather

have also been

(30)

from insertion

and 1H nau data

with

CPtH
group by protonation

arising

(28) into

of cyclic

-i

(R = Me, Ph: R' = Me)

by this research

The

has been

of type

trans-[PtH(MeOH)(PCy3)21PF6.

hydromethoxycarbene

prepared

the

PF6 + MeOH

[821_

nitrogen

carbene

stereo-

that for JptCNC

-

complex,

trans-[PtH(MeOH)
of

than that of a trans methyl.

yields

derivatives

and chemical

[80].

lPF6 + Hhm

the

cis orientations

carbenes)

converts

is extended

the

between

have done a sim.milarstudy

and it is noted

A

has

(R = Me, Cl, I; L = AsHe_,, PMe,Ph;

to Pt is greater

178:.

for X, vith

occur

adopt

Coupling

authors

N and 0 heteroatom

The general

of (29)-

rings

groups-

These

are discussed,

of a series (81).

constants

o and r Interactions

methyl

[79].

by treating

1,3-dipolarophiles

trans-[PtHe(C~C6H~X-E)]PFg

The phenyl

ring.

[PtR(carbene)L2]PF6

is a range

described

complexes

that both

data are reported

complexes

in high yield

the respective

of the o* substituent

deduced

tith

been prepared

with

_

.[Ptcl(CHNMaR )
4sq L

-

IPt<~R~L
e2Cy+y

-i$%lka&..
pph+ diaaoalkane

= 9-diazofluorene.

450 dipllenyldiaeoMthane) of carbene

X = BF4. CF3SO3-)

L = PPh3 PM&h=; sulfur

a fluorenylidene

of the thio esters

carbamyl

complex

CF3SO3H

IV_

by treating

Internal

benzaldazine,

organic

[Et301BF4

(R* = PhCH2,

CH2=CHCH2,

1861.

of o-palladation

(34) undergoes

hetallation

c-netallation

(35) [87].

Compounds

X = BF4)

the appropriate

have

halide,

or

products

to prepare

crystal

-C3H4 cpPd/a,

of heterocyclic

phosphite

resulting

The

of the phosphite

A single

a range

of trL-Ftolyl

of alkene.

from azobenzene,

1-methyl-1-phenylhydrazones.

dimethylhydrazone. has been used

(33) via an elimination

compound

H;

NeHg,

at

or thio-

or MeOS02F.

with

W-fez;

by alkylation

reactions

of a series

benzylamines

compounds

compound

vith

A series

SEt,

or PtCl[C&)SEt]L2,

the thiocarbamoyl

acetophenone

and tertiary

[84].

Y = OMe.

[t35].

metallation

Carbonylation

Et;

have been prepared

PtCl[C
for the latter

is obtained

< R = Me,

PtCl[C(S)ORe]L2

[PtC1[C(SR')Nne2](PPh3121X been prepared

complex

[PtCL[C
complexes

occurs

halo

by HCl elimination

structure

of a complex

with

complex

to yield

Pt(TP)(TP-H)X

L

t

cpPd' 'Cl

(33)

(34) (35)
(X = Br, I.; TP = 2-(2'-thienyl)pyridine) two pyridyl an iodide

nitrogens

1881.

The ferrocenyl acetate

to give

Na2PdC14

mutually

The sulfur derivative

trans

shows

to each

atom in the thiophene

C5H5FeC5H4CH2BBe2

the internally

+ C5B5FeC5E4CB2N&,

the platinum

other.

metallated

ring

reacts binuclear

coordinated

a thienyl

vith

carbon,

to

and

is not coordinated. Na2PdC14

species

and sodium

(36) [89].

Tbe

-

(36) dimer

can be cleaved

vith

did-(2-atoarpl)Pd:cap

acac. PBe2Ph.

AsMe2Ph,~P(OHe)3.

be .obrained-in

-.

PPh3.

Compounds-

good.yield.by:,treating.._..:

..-._:.i

451 Pdq(dibenzylideneacetone)3 series

of 9-metailated

dimethyl

yellow,

[Vl].

New 6-membered

the internal

and amides.

studied

metallation

osatones

of

and Pt
The mechanism

with

have been These

LiN(R1)C(R2):%Rl

metallation

reactions are shovn.

is considered

aroxybenzene,

isolated

dimers [92].

and Pt(I1) features

[93].

PhCO&ZSHS

with

osazones.

The

complexes

betaines

coordination

of

for the

of halo

gives metallated

to involve.initial

by

with

has been made

found

Treatment

A

and

can be cleaved

can be cleaved

of Pd(I1)

[go]. and

from the pallada-

A study

Ano~lous

are discussed ylides

compound

from Li,PdC14

from 4.4' -azoxyanisole

ring compounds

Tlacac,

transformation

Pd(II)

mercury

have been obtained

The dimer

tion of N-aryl-amidine NaCp. allylMgC1,

the corresponding

4.4'-azobis(N,N-dimet.hylaniline).

4,4'-azoxyanisole Tlcp.

with compounds

of

[94j.

of the ylide

H-$Ph [MCl,(L-H)(dmso)]

M-Cl

(

!-Ph Possible intermediate

iV

[MCl(L--3H){P(OMe)& (i) -HCl;

followed

by intramolecular

are formed PdC12L2

with

(ii) dmso;

electrophilic

Pt and dimers

IL = PRut(benzyl)2,

(iii), -HZ;

attack

(38) are obtained PBut2
(iv), P(OMe)3.

by the metalwith

Pd.

only undergo

Monomers

Complexes

(37)

trans-

in_ternal metalla-

tion with difficulty[YS],with the former ligand being the most difficult. Since

the analogous

metallation

under

compounds

mild

PBuZt(c-tolyl)

conditions

to form an

steric rather than electronic

differences

for the failure

of the former

ligands

..._

:

___:

-

and PBut(~-tolyl)2

undergo

analogousS-memberedring,

are considered

to undergo

to be responsible

facile metallation-

452

V

anz’ thiocarbonyls

HQ~+J~carbmyls

componnd ~-tpM(Co),Sb(He)2Ni(C0)3

has been prepared by treating Infrared

w .th or-cpM(Co) jShHeZ (;I = cr,M6,W) [%I. A series

a -e tabuXated.

hive been prepared Tie phosphinos (3 I si,

The

dsxivatives

reactions,

Tabtlated 13

infrared

C nml spectra

ii

constant

Y in the ligand,

has an additive

c wbanyXs has been repcrted CK$‘h.

PCCl*(CDI (AsEt3)2, clarge

for a series

are teported

For

effect

ahfts [49].

,

C) fall

inPlueacr,

the v&bee

the infrared

plotted

against

X of htgh

vaage btueea

ligsndn,

meries

chemical

shift.

B-[PtX(CO)L2]BFq

L - pEc3, PPh3, A&3), ehifte

decreaeea

sensitivity

trams

Both the and the change of

group la platinum

the chemical

in IW range of 960-990

The data

against

in each case.

ehifc

The chemical

but shows little

HXatxde

l J(qp

I;

and PCl.3 (R *

OPh) [981.

on Ute carbenyl

For the

~nNl(C01 4,

plotted

of the cnrbonyl

NCS. NO.,, Br, Cl,

of

and also

by phosphine

end {Bpy][PtCl,[CO>)

on the complex,

c fs ligands .

are found

of carbonyl

T,e ‘3 C nmr data forchemical (C = R, C6’lqCl,

shift:3

Ear the carbonyl.

Good correlations

repkc&tent

[97]. P(KMe313

alaag with the band assignment

Ph; Y = Cl., He, We,

and the I” C nmr chemical force

K&bachnik’e o.

cxu3tants

data,

(n = O-3) where L 6 PR3. PPhZY, PPhY2, p(OR’)3

tabulated

etquential

on the tetracarbonyl

have been obtained

I%?, Pr, Bu, Ph; R’ * He, Et, Prit aretching

compounds

used are P(CMe3)3, P(C14e3)2E13eJ, P(Clle&BMe3)2.

Ge, %I).

given.

data

of tricarbonyl(orgaaophosphfne)nickel(O)

by substitution

Ni(C014

asd maas spectral

bfLiaence,

and coupling

with increasing to the nature the veluee

I&, hut For lAgends

1658-1157

8s.

e-

A srrias

of

of the for

of

luu ttdrms

453 cyanocarbonylpalladium(0)

complexes,

Ba[Pd(CN)
isolated

have been

liquid

NB3 and precipitating

Values

of vCo in the range

square

planar

giving

a dihedral

]PtC12(CO)]-

sites

i has a strong chemistry

angle

The following

on the Pt-Cl

influence

derfvatives

formed

C02H.

COMe.

effect

on u
v(C=O)

for a series Et2S0,

tions with

v(Pd-C)

bipyramidal

metal

of complexes .He2S0. Begs. and values

cluster

crystallography

trigonal

cluster

fragment

is symmetrically groups.

influence

capped

atoms

PtC12(PPh3)2

Variation

on v
[102]_

of

for compounds

of

Pr2S, [104].

Correla-

A trigonal

(39) has been

investigated

(39) can be described a planar

interactions

as a

Ni3(C0)3
to two identical

(CO)5C02(CO)2Pt2
(411, and Pt3(C0j2(PPh314 with

Ii, Cl, Br.

of R has little

The values

reported

in which

compounds

(n-cp)2(CO)2H02(CO)4Pt2(PPh3)2

and a number

reactions

spectra

are discussed.

by Ni-Ni

the

of 2.584(2)

A study of the

(L = thiolan.

The structure metal

New cluster

by treating

[103].

Et2S) have been

[105].

lengths.

R = Xii2. ?le, Et, CB2OH,

[Ni5(CO)g(u2-CO)3]2-

of transition

occupy

distance

has been made,

and Raman

PdC12(CO)L

of v(S=O)

bond,

EPtHCCO)
Infrared

CO; Y =4-R-py;

distorted

Pt-Pt

in the carbonylation

CN) have been studied

by X-ray

been obtained

bond

[PtN2H
and only a smell

The structure

groups

The Pt-Pt

from the carbonylation

Pt3
C02Et.

(401,

to be

atoms.

of platinum

to arise

(X = C2B4,

apical.Ni
The carbonyl

trans

IPtN2H(PPh3),l,CBF412:

trans-PtCI2XY

[loll.

[100].

CO in

cation.

of two slightly

by an unbridged

metal

are prOpOSed

Pt(C0)2
consists linked

PKePh3).

with

the appropriate

cm-' are found

entities

of 60"

are suggested

.(PhCH2)2S0,

1780-1790

(R = PPh4.

K2[Pd(CN)2]

with

on the adjacent

of hydrarine

of species

the complex

in INPr4 "I 2 [Pt2C12(C0)2]

of the anion

transoid

R[Pd(CN)(CO)] by treating

Na[Co(CO14]

or

(42) have

SJ,l[(~-cplMo(C0)3J.

The sfmxtutes

are based

w, th substantiating

prelimminary

IT.5 X-ray structure

of xzompoufid (40) has

[107J.

The reactivfty

X-ray

3f cationic

OR infrared

results also

thiocarbonyls

for

(40)

spectrtiscopy, and (41)

been pubLished of platinum

[106].

separately to nucleo-

PK,M,I,

~cbHS)3p,

\

Fhiles

has beerl used tx prepare

compounds

113) and (44).

i

When a solution

455

for l-2 days, the compound [PtCl(PPh3),(CS2)pt(PPh3)2)BFq X-ray

study

shows

precipitates.

the compound to be a metallodithiorarboxylate

An

complex

[lOS]. VI.

Metal olefins Treatment of K2PtC14 with 2-propenol,

yields

initially

the complex

-cis-PtC12(diolefin) cansidered to arise

[109].

The resultLng

from the series

+ CH2=CHCH20H

[PtClJ-

2-butenol,

[PtC13(olefin)lu,

olefinic

by a tearrangment

ether

complex

(45)

to

is

reactions:

IP~cL~(cH~~cHC~~~H)I- + cl-

z==E

iPtCl,(CU2GHCH,OH)J”

of

and 3-buten-2-01

followed

+ CH7dHCH20He

+ Cl

PtC12KhHlo0~

-

+ H20

(451

Compounds ptC12(C2W4)(N-N)

have been prepared

vith

nitrogen

a series

of chelating

compounds lose yield

ethylene

A repart

[PtC12(C2Hg)]2, Pt(II)

Alkylallyl

has been publiebed which converts

undergo

PtCL2(pyI IR(MeAGCtiw$,1 ia dependent

[ml.

were! made using

themodymmlc

stability

Phorochemical

elimination

‘I

tm

the chlral of the

ad

of olafin

PtC12 to give

with HCl [112]. [PrCl,]*-

Nalo-

and Etch t1131. complexeS

PdC12 [114]. o&fin

Two

to Pt(If)

in w-

of each diastereomer

R grotip;

CD epcctroacopy.

of cis_IPtCI.(C2Hq)(?iX3)Z]+

4th

to form n-olefin

The proportion

on the bulkiness

virh Me3SSCH2CWCH2to

reacts

ICnH2n,lPdC1]2 vith of

salt

These penCaco0rdfnate reacts

to H[PtC13(C2H4)J

form on complexatim

of Zeise’s

and [PtC12(Me351CH2CH-CH2))2

that C2Hq

ether abstraction

tCnH2nPdC12]2 and rr-complexes

assign*ente

by reaction

compounds have been obtaLnad from

ethers

diastereamers eolutian

salt

Zeise’s

compounds K[ptCl,(Me,SiCH,CH1CH2)]

[ill]. olefin

[IN].

ligands.

in

the configurational Polarography

atid

has been studied.

from PtCIZ(oLcfina)(aPaine)

ie facilitated

by increasing

hu

-

ZPtC12
the substitution

PtC12(C,Hq)L

Pt2C1&(amine)2

on the olefin

(L = py, R-anisidine, dimers

PPh3,

+ 2 olefin Compounds

11171.

PEt3)

Replacement

cleavage

of the resulting

butene-2

in trans(N,olefin)-chldro-L-prolinato-trans-butetn?;Z

by ethylene.

platinum(I1)

AH' = 10 K cal mol

nucLeophile

and the coordinated

is a very

determining

ease of substitution.

Na2[Pd2C16] Na[Pd 2

+ olefin

Cl (olefin)] 5

been measured

in acetic

ligands

Stability

_K1'

found that again

two complexes These

formation

Pd(OAc)2

with

and reaches

discussed. [121].

acetic

the oxidation

study

of octene-1

PtC12(C2H4)L

used to demonstrate of trans-PtC12
cis

HC1 has been used Pt2Ci4(alkene)2

to synthesize

(alkene

show

absorption

two W

bands

of vinyl

is catalyzed

by PdC12(PhCN)2 %

[123]_

causes

spectra

which

of

and

Irradiation

isnmerixation

compound

to

complex

11251.

by

Complexes

3,3_dimethylpentene-1,

and the %I -

exchange

by

nmr data on

of a.haloalkylpalladium(II)

prepared

the

has been presented

with UV light

Alkene

and

vith

Rate laws are

L exchange

= 3,3-dimethy:butene-1,

[X26]_

EZectronIc

Y'= A-R-py)

[122].

pyridine)

and/or

has

to be nonstereospecific

a haloalkylfuran

have been

discussed

monomers.

olefin

Ring opening

3,3_dimethylhexene-1) compounds

by R-benxoquinone

(isoquinoline)

[12&l_

isomer

acetate

of the catalysis

(L = substituted

halogen,

inconsistent

is 0.2 M.

is considered

is reported

of chain

Pd(OAc)2

The rate of exchange

[NaOAc]

have

+ NaCl

Na[PdfOAc)5(olefin)]

to give vinyl

when

and acetoxypalladium

A kinetic

complexes

a maximum

in

+ NaCl

study with

find the data

[120].

acid solvent

factor

Kl and X2 belov

to be independent

are found,

authors

the olefin

[Pd2C14
A similar

[119].

of Pd2(OAc)4(olefin)2

propionate

between

constants

and are found

acid,

(C5-CQ)

Na[Pd(OAc)3(olefin)].

g2

+ olefin /

and AS' = -25

important

Na[Pd2C15(olefin)]

length of hydrocarbon only

interaction

by

of trans-

order rate constant with -1 X-1 to -46 cal mol _ 11181- The steric

shows a second

cis-

have been obtained

of these

is preceded

of trans-PtC12XY

are sensitive

asymmetric

by dissociation (X = C2E4,

to R 11271.

of

CO;

One band

is

l

a ligand PY-

P--H transition,

13C nmr spectra

and the second

are reported

(alefin = C2E4* acrylonitrile, maleate,

maleic

anhydride)

and other measures although

anain

Rx.

identifies. t&. CC

for compounds

fumaronltrile,

[US]_

of back-bonding

exceptionswere

are allnear.to.160

is a CT transition

A rough

between

Pt and

Ni[P(C+-tol)3]2(olefin)

methyl

correlation

euch as v(C-C)_and

acrylate, between

dimethyl g(C).

d(C=C).exists,.

T

457 1243 cm-l.

The local

electronic

as the core of a doubly near-radical-cation spectra,

bonding

from ethylene increases

modes

and hence of bonding

to prepare

species

trapped

criphenylphosphine acceptor

ligands

Crystal Pt(C7Hlo)3 preparative

trans

by electron stabilized

structure

resulting

ring opening

N%(O) with

for these

L = PCy3;

11321.

aldehydes

reported

M = Pt, L = PMe3,

<46).

:

_

.-.

compounds,

Pd
Pt(f1'4-bicyclo[2.2.0]hexene)(PPh3)2

[130]. shov

that

application

from trapping

a The

of quadricyclane. Complexes and ketones

to

has been

of as li-

[133]-

data has been

procedures

ligand

bonding

are of limited

poor olefins

reported

C2H4 and Pt(II)

Ni
compounds

that the

than one type of internal

for Pt(C,F4)(C2H412

(46) and

[134].-

In addition

to the

the authors

also report

the

(47)
of Pd
..

for ethylene-Pt

wavenumbers

of organic

or as a

by the o donation

between

of L, the trans

from more

from a catalyzed

have been

is dominated

The compound

[131]_

is regarded

to the conclusion

strength

force-fields

isolation

_-.. . -

leads

Pt(II)

are derived

ethylene

of the free species,

of 'H. 13C nmr, vibrational

influence

vibrational

a number

intermediate was

anion

and the bond

of approximate

discussions

reactive

to

of ethylene

coordinate,

used

of coordinated

Hiickel treatment,

decreasing

of the normal

state radical

Correlation

to platinum,

with

Calculation many

[129].

and extended

coordination

excited

Pd(C2H413

The crystal (48) shows

or 4, M(C2H4)2L structure

(M = Pd.

of

a long distance

for the

458 CC bond of the coordinated betveen

olefin

the PtP2 and PtC2 planes

(1.52 &. [1351_

and a dihedral

The crystal

angle

structure

of 3.2"

of a complex

(48)

Pt
2

by this author, betveen

(C4F8

= octafluoro-w-butene-2)

shows unusually

the PtP2 and PtC2 planes

long C-F bonds is 10.8O.

(49), previously [1361.

The dihedral

and considerations

:._

reported angie

of bonding

.

459 leads

the authors

A neutron

for CC [1371_ hydrogens

to question

The structure

appropriate.

of ethylene

the C-C bond

free rotation

obtained

temperature

of TCNE,

[141]_

The

cyclonona-l,5-diene) treating

product

is

found

from

dipalladium

(50) has been

the

dienyl

by treating

The complex with

slowly

to platinum ligand

prepared 11453.

are fluxional

rearranges

[1463_

have been

Pd atoms

at low

to repeat

the

the

n.n-complex

with of

e.

trans-1.3-:

dependent

11421. = z,

compounds

4-

and The

e-

result

from

the latter Possible

reaction structures

are

di-p-chloro-(l-4.5-n-7-chlorocyclaoctenyl)

a-bicyclo[S_l.O]oct-3-ene

complex

mechanism

of N,N,N',N'-tetramethylethylenediamine

of the product

The compound

coordinated

the

trans-1.5,9-cyclododecatriene)(CDT)

presented.

o-cp rings

as

Unusual

to [
compounds

vith


trans -*-

of

due to a

to 1,5-cyclooctadiene

to be solvent

corresponds

n-allylic

where

to be likely exchange

-cis-1,3-:

[143]_

or Ni(trans -*

in the presence

reported

of the failure

identified

of e,

is reported

The stoichiometry

the olefins

has appeared

[klC12(diene)ln

Ni(l,S-COD12

lithium

The lengthening

and Pt
4-vinylcyclohexene

has been

of compounds

[1381.

the

of C.,F4 and C2(CN)4.

than to a dissociative

Rearrangements

1,4_cyclooctadienes synthesis

of

is D of 1.45 A

salt show

is considered

by treating

A report

(1401.

vinylcyclohexene.

[144]_

rather

Pd
rearrangement

PdC1Z
complexes

model

a distance

of Zeise's

from the Pt atom

of the isocyanides

on the gram scale

published

study

shows

Ri(TC&X.Z)
of complexes

Compounds

[139].

with

bent away

equivalence

the Dewar-Chatt-Duncanson

diffraction

is less than in metal

A series magnetic

whether

of Pt
by treating Complex

PdC12(PhCN)2

(50) slowly

Pt
a lov activation

to a further

and a further Compounds

The

compound

and in solution

(52) having

cyclopentadienyl

<53) <54) and

the palladiacyclopentadiene

to a

(51) is reported. energy,

o-s one

with

rearranges

the

a n-cp ring

group

attached

(55) have been Pd(C4R4)(bipy)

to

prepared (g =

480

(53)

uith the appropriate N,N-dicblorosmine eompkx

C56) 'has been prepared from NIC12
derSvat%va [X481- The compound gives a substituted benzene when treated with dimethyl acetylenedicarboxylate or di.phenylacetylene,and tetraphenyLIcyclopentsdienoae on treatment vith CO.

Reaction of C6(CF3)6 with

crianRuLo-Pt3CBnrNC)6or Pt(PhCH4HPh)(PKe~2 Rives the metslkxyclohepta* cts cis cis-trgenes Pt(e(CF3)=C(&F3fC(CF3)=C(CF3)C(CF3)~'t.(CF3))L:!. The -*4-w..-

461 complex

vith

L = ButNC

ystallography

11491.

Ft3(ButNC)6

(57)

has been Treatment

structurally

investigated

of Pt(l,S-COD)2

[150], and vith

PCy3 or C2H4,

with

by X-ray

Bu'NC

Pt(PCyj)2

cr-

yields and Ft(C2H413

respectively.In similarwork with-Pt(0)compounds.treatingPt(PCy,),

vith H2 the compoundPtH2(PCy3)2is obtained. A series of compounds formed when

Pt(COD)2

ethylene

11511.

platinum

atoms,

hexafluoroacetone, 1.96 i.

Uhen

is treated

The molecular 0 2.585 A apart,

with

hexafluoroacetone

structure vith

of Pt2(C(CF3)20](COD)2

shows

one bonded

to the carbon

atom of

Pt-C 2.08 A, and one bonded

to the oxygen

atom,

_ 0

Pd
is treated

are

and tetrafluoro-

vith

two moles

tvo

Pt-0 = of

462 butadiene

a new compound

beatcquloone)Lz the

1H chemical

(58)

like

obtained

of

shifts

benzoquinane

and v(COI of

the

rhe

lfgand

phosphorus

monomer

ha-s been

with

F

(601 complerq?s

F

lldl

PdlPY'h;':

F

a duroquZnone-

uf

these

metals

are

presented

compunds

r

F

F

F

lIlIlI

e

1

F

F

+-

[l-54] d ~Jhcrt ?((PP~I~)~ he: I-2,5-dione,

(un = methylcnec!rclopropane,

Pt(un)(PPh3)2

F

of these

FLYiIz.L

F

the

2Pd

al

sclved

hexafluorobicyclo[2.Z.aI

(591 an4 dlmer

The l9 F nmt spectra

I

wtf,n

dicarhanyl~l,4-difluoro-Z,3,5,6-tetramethy~-l,~-

04 = Pd, PC) SS trea’;ed

Complexes

The structure

(153 1.

Pd(EP(OPhl,l

correlate

Wh3)

dihoracyclohexa-l,5-rl3enyl)nickel(O),

tl551.

For complexes P(CaHkCL-~)jr

*~-------

complex:

both

[152). 3, PPh3,

(PPh$$d

ba5icity

is

[L * PBua3~ P(W6HbUe-E)

are

obtained

an.3 discussed.

t.r3ns-2,3-dlmethoxy-

[Pd(Ph3PIJ]

(59) J

(60)

carbonylmethylenecyclaprapane,

-cts-2,3-dforethowvcarbanylmethyleaeand tr,r-(PtC12(un)py] (un 0 & or a-2.3”dimethoxy-

cyclapropane)

have been

rarbDnylmethylenecyctcrprQpane) nethylenacyclopropae Campre hens ive dimethyl-

inert

+-I and 13C tmr data

ring

1.50 i betueen palladatioa

remainns

the

is

prepared, toward

given.

upon

intact

coordinated

The ?-bonded

heat

and W radiation

Crystal

structure8

outaide

1Pethmmlgafa

the

mmrdination

rrphere

ou s 0% bond of MCi

fl.591.

Laetyl

atom

givea

pracmd# exclusively

bromfde

(0) with

coordination,

carbon

aE l,%cyclooctadlene

oxypalladaciaa

-chmism

are

and 3-Pethyl-cycloprapenebie(trbphenylphoaphine)PE

cyclopropeoe

frw

Sfgauds

of

the *ring

a ttans

product,

wlch

attack

of

pnl’adium

jfioflSs~adf~*)

2 reacts

with

of

L,Z-

shou

the

a C-C distance [1571+

of

Hydroxy-

indicating

by the nucleo~hile 11%).

(1561.

Kinetica

that (water) of

&EGG t? coql&~ad

Pd(dba),

to yield

a&t insoluble

PhCH-CHC-CHCPhHCH(COMCJ~ EA -ku+CH=CnC’CHQPh~

polymer

(61) which

[HO].

Enthalpy

trans-1,2-Ph2C2H2

VII_

Metal

> a-1,2-Ph2C2H2

Pt(ArC%CAr')(PPh3)2

Ar = Ar' = 2-py; coordinated

the fluxional Pt-olefin

> PhHC2H2

5-diketoaates

bond strengths:

11611.

(Ar = Ar' = Ph, Ar = Ph, Ar' = 2-py;

Ar = Ar' = 2-(6-Me-py)).

to Pt, have been prepared

coordinate

The X-ray

to prepare

show relative

acetylenes

Complexes

will

can be cleaved

measurements

to the compounds

stxocture

with

(1621.

through

the acetylenic A second

the chelating

of (PPh3)2Pt[C2(2-py)2](CoC12)

a tetrahedral

coordinstioa

(PEfe2Ph?2 <%

= %

about

y 8, He: CRI&L

~Pt(Gs!ccE2cE12011)2(Plfe2Ph)2, tf-~PtX(irtolypLaCetpllde)(~ ~_ _'

metal

triple bond e.g. Co, Pd

pyridyl

nitrogens.

has been solved

showing

Complexes

traas-PtCEC~~CW312

= cyclohexylidene;

It2 = H. Me, Ph),

CofXI).

trans-Pt(~tolylacetylide)2(P?fe2Ph)2,

2Ph)s have been prepared

using

the sodium-

464 tertiary

hydroxy

Analogous

dehydrate

vith primary

the Ill nmr spectrum

Subsequently hydrazine

found

that these

to dialkylplatinum
vith HCl and details

compounds

groups

with

Ac20/pyridine

do not dehydrate

but give

is discussed

to

of trans-Pt(C~Cc;H2~H20E)~~~e~Ph)~-

these workers

hydrate

to eukyne

hydroxyl

is given IIand the use of Eu(fod)3

13C nmr data

acetates. analyze

compounds

compounds

13c. 3%

+ N~H~-H~o

trans-Pt(aR)2
acetylides

compounds

could be reduced

(62) 11641.

nmr spectra

by

Reactions

are discussed.

-L trans-Pt(CH=CHR;2
(62) (R = CH20Me.

&dative

addition

Che20U,

of RC3Xl

compounds

PdH(mR)(PPh3)2

in liquid

ammonia

Ph)


or methylamine

yield

CH2=CMe)

to Pd(PPhB)4

Alkali

tl651.

metal

react with &-PtC12
gives

acetylides

to give monomers

where R = H, He. Ph 11661. Use of excess acetylide -cis-Pt
Compounds

yields cis-[Pt(E)2C6H4(DPE)]n.

give polymer

A number acetylenes.

on treatment

of articles A complex

[NiH(PCy3)2L]BFA structure

vith

describing

Ni
is proposed.

HeCN)

trans-PdWZC-CECH)2(PBu3)2

[1671_

have appeared

(L = Me-py,

CF3

CuCl-O2

cyclization

(63) results

vith

CF3CECCF3

from

11681.

ltrelve and fourteen-membered

reactions

treating

A cyclic

ring organic

of

trans-

ring compounds

CFB

(63) have been

prepared

from a.m-dodecatrienediylnIckel

enedicarboxylate

[169]_

Complexation

gives a n-olefin

complex

vbich

furar_ring

proposed

s-bonded

[1711-

cyclizea

to palIadium(I1)

and dimethyl

of He3CCWXe2OH

with

to give a further

[1701-

In a study

acetyl-

PdCl,
complex

with

of the products

a

465 of ButCXH,

rhe first

acetylene sequence

Pttco&cl,

+

11731.

The structure

of reactions

Et-CIC---Et

step occurs

with

cis-chloropalladation

of compound

of the

(67) has been solved

given.

Et~.?UF.CgU6

WY=%

(66)

1

-

CCZAI (61)

.,. .--_

:

-.

and a

A number of othex epclr:ed.

The coa+e,

,O” from linearity .ength

of

acetylene.

acetylene

1.277125)

prbsition

for

Irond length

show dkhedra;

:arbon distances structnres

Is 1.227(10)

an&Ice of 4.413)

1.29118)

of bond

Theheseauthors

[17&l,

the platinum

i.

coordination

axe zis-bent for

the

* cyclortexyne;

C7H1*

acetylenic

i respectively

[176].

away

phenyl.

The structtires

and 7.9(3)“,

i and 1,283(5)

deviation

The

of cyclocarbonThe cryeta

of WI,~CXIX,,~CF3C2CF3~3(bt3) and NIL~(CCI)~(CR~C~CF~) (C~JB~I I6c))

show the compounds to be clusters (63) is wlrsual

lher$etics trfad

i

He and 21.2(9)”

the

have been

+I?? carbon-carbon

s~bsttt~~ents

It W&l81 /PPh312 and PJ.K,RlO) (PPh3T2 (C& lepryne)

complexes

OWLZClW il.751 A Assuming a

the acetylene

of

The acetylene

1 .7(1,0)’

triple

:arbon-carbon

is

of PtMefEt2B(pz)2]

$eomerry is square pl;~n.ar. Iram the acetylene;

of alkyne

the caordinated

the structure

caordinarion

strtictures

Pt(MeCECPfi)(PPh3)2 show9 an expected

fot

cootdinzted

the

rlso report ilngle

crystal

ti

of tetctiona

have acrracced

[177].

The cycloocratetraene

rjng

in

beiug planar. isoolving

mm2 attfmmifk.

acetylenes A ~~~ckmism

and compounds of hali been presented

this for

467 the decomposition vith

of PtClMe(bipy)(Me02CCJCC02Me)

loss of MeO2CCXCO2Ne

[178].

The rate

(70) to PtClMe(bipy)

is first order

(71)

but strongly

(69)

(68)

solvent which

dependent-

k

The data

= 0.0122

1 The enthalpy SCHEME

min -l, k

is rationalized in the following scheme for -1 min -1 and k_2/k3 = l-65 J IO4 lmol .

= 0.179

2 of the reaction

AQ8

(NN = 2,2'-bipyridyl,

of PhC2Ph

with

Pt(C2H4)(PPh3)2

R = Cope)

R

Me

C’ \Pt' ("

’

N'I'C Cl

II

Me

++ 1 FL

\R

Ci

-82~2kInwr1 crystalline.

is

[1791-

Ethylene

The entbalpies

+ RCCR

N\Pc/ -(

Cl (71)

i-T

fast

k3

+ Cl- + RCCR

M

is gas phase

of reactions

and other

between

reagents

EC1 and Pt
.

hme

been measured,

energies retry

aad

PC-K (X = Cl, complexes

used

to set

PhC$Ph,

NiZcpZ(KCZR’)

up a table

C(Ph)=CIfPh, decompose

Pt(PhCaCPh?IPPb3221rryat)

v

Hetel

II.

of

t 1s addition

4 eating

r~~-allyLSr:

camplexes

of PdH[PhpECH2CH$Ph2j’

an insolutlle upon

;t: 16 W mol-’

or fragmentation

[03-C

about H PtiPCy

35

of paJ.ladium (E = P. As)

($f * Pd,

compound

treament

fluxionality of

f m--CHPk=CHPh(g)

of R groups

have been to

l,3-dimes,

and cyclododeca-1,5,%triene

M(dfbentylidar:eacetone)n

M:arac) (CP$)

slectrum

of

+ 6 kJ mi&

fragment,

cyc3ohepts-J,3,S-triene

P r3CC1 gives

5:udy

of cpNi

loss

[lgll.

Allyls

A series

1 S-dime,

loss

of alkyne,

spectra-

+ PcCL(CP~CHPh)(PPh3~2(cryst)

AH - -139.0

c;,clopentadiena,

In mass

-+ _cfa-PtCla(FPh3)2(cryst)

[PPh.$ 2 * 2HClt&

Pt (PhCxPh)

(lgC].

by loss

+ gCL(g) AH J -90.2

of bond dissociation

Phi

with the

TlCacac) .

triphanylmethyl 1 ]P’P

32

n * 2; M = Pt.

[MC1(CPh3) ]o which

6

shows

11821. II * 3) with

converta

into

H and I3 C nmr is used

%tiAtiC”

11831. 3

by

cycloocta-

x

ligand a

prepared

rl -311~1

to

The ‘H nmr 5tructute

at’

469 room

Non-equivalence

temperature.

Ibis magnetic temperature. rotation of the PCy3 groups compounds

Pt(21Ie

nucleophiles solution

insertion

SbF6)

reaction

have been

and apparently

a relative

Reactions

of I-. NO3-. discussed

prepared

which

anion

dependence

Stable

11861.

11871.

Air stable

are good

a nl-allylic

even

(Rl = H, Me, Ph; s

at

in the scheme. (X = BF4. PF6;

and general

complexes

complex,

reaction

(72) have been

in the presence

of phosphines

complexes

l14TNi(PPh3)2]

PF6)

in

structure

is first order in initial 9 of SbF6 s BF4 > PP6on AH

n-allylnickel rigid

of

are dynamic

is outlined

py, CO, PPh3 are described,

are structurally

and phosphites

A series

of trans[PtMe(n-allene)(PHe2Ph)2jX

and shows

at room

to the restricted

Bases which ubich

have

mechanism

to cis-[Pt(r-2-Meallyl)(PHe2Ph)2]X

schemes

is observed

[184].

prepared.

1rI adducts.

The proposed

11853.

protons

is ascribed

the Pt-P bond

give stable

at room temperature,

low temperature The

about

allyl)(L-L)

to Pt(I1)

of the syn

non-equivalence

= H, Me) are obtained

X

in high yield

(' = 'lo"

by treating

[Nil. -

-.

cH4HcH=cH2 NgCl . 1 INil l-

(72)

%Pb?W,

L.?

I L Ni-C6C15 I PPhMe2

-butadiene *HC6C15

1

[Nil = C~C~SN~(PP~-VET~)~C~

Ni(CO),

vith

[1881.

_A high yield

-using

salts ~[k2CE~CE20P(NMe2)3]X

nickeLhalides

._

synthesis

and conjugated

Cl8?l_:_._~~~'chlo=~~(~~*y~y~) yeo&%'(i73)

folloved

of rr-allylnickel

IfiiCh~c$nb_e-converted

dienes

by addition

complexes

in the presence _+mer

$th

of PPh3

haa been

reported

of metallic

norbornene

t&the-chlorotriphenylphosphine-

zinc

yields

a

1

nickel
with

derivative

substituted

(74) with

cyclopropenes

PPh3[190]. leads

Treatment

of

to the formation

of

PPh3 +

xe

>

C7Hlo+He

Me 3

(74) indenyl

complexes

Compounds

of type

(75)

in addition

R1 = R* =

ph,

R4 =

H

R3 = R4 =

&

ph,

R* = R3

Ph,

R1 = R* = R3 =

&_

R1 R* R3 =

Ph

E

n-ally1

complexes

"-CtI=!:C6H4R-~)]2 [Pd(l-3-n-allyl)(E-RC6H4‘.--

R1= R2 = R3 = R==

to open-chain

r

5

9

R4 =

&

R4 =

Ph

R4

fi

s

C1911.

(R = H, Cl,

R1 = R4 I He, R* = R3 = Ph R1 s R* = R3 = R4 = Ph

Ne) are formed by treating imidido)

[192],

[Pd
TuocouformersexSst.~

with

Li(N,N'-diarylforma

AC SO-lQO” ape conformer

undergoes

an intramolecular proc&3s~bringi& the ally1 group to e&valenc&.and

a

mechanism involving inversion of the C2N4Py2.ring,via a chair confomation : is proposed. ~di&&&&ctim$L tirk &-be& d&e oti. these tri&endo allylic sys~ems~[193].~:~Chlorobeniylpalladitlm
-.. -1.:_-_. .

: _

I

._ _

-_:‘. ._ ...

Pd atoms

f

(76) obtained

in good yield

by treating

temperature

matrix

of articles

in Aneevandte

from treating vith

the first

undergoes allylic most

bis-a-allylnickel active

tvo groups

the c-ally1

group

complexes,

atoms

chloride

is discussed

compounds.

attack

at the s-ally1

reversible

(78) in addition

z-pbenyl

derived

methylene

of the nickel

spontaneous complex

stable

The use of metal

benzyl

in a low

in a series

Chemie one of vhich [195] discusses applications -* of nickel allyls. The distribution of organic products

to the synthesis

allene.

[19&l_

Pd atoms with

allylic

complexes

amines.

site, whilst 11961.

ring closure

(79).

and has shovn

aldehydes

The o.n-complex

to give

to an irreversible isomer

from isoprene

and aldehydes,

attack (77)

the e-phenyl

ring closure

The crystal

structure

to the of the

at

472 acetylacetonate measure

derivative

of the ability

mediates

chelation

by

of (78) is reported

of a coordinated has been obtained

CPh3,

CH2PhI

11981.

A quantitative

to stabilize

from a variable

study of (n-2-methylallyl)Pd<2CR)(PMe2Ph) CF3, CMe3.

[197].

carboxylate

[R = Me. CH2Cl.

The order

of increasing

ioter-

temperature

umr

, CHCl,, CC13,

AG'T

(R = Me < c

(78) CH2Ph

< CH2Cl

decreasing

c CF3)

ability

as a chelate. from

Treating

diallyl.

n-crotylnickeL

decomposition FdBr2.

and Pd [201]_

MeC 3

NiI(C3HS)L

halides

exchange

ligaud

with

of [PdBr(C3H5)]2

a

the carboxylate

and ally1

iodides

and i.S-alkahienes

gives

with

SBu2) have been prepared

and Et2G do not react

alkyl

to form 2-alkeoes

is in agreement

to stabilize

(L = PPh3,

and L; THI?. 1.4-dioxane.

at the CH2 group

thermal

proton

of the oarboxylate

Complexes

[NiI(C3H5)12

mainly

for 3,4-allylic

ally1

bromide,

(199).

gives

attack

[2001.

The

benzene.

and Pd; ubile Complexatiou

[PdI(C H )'I gives benzene. diallyl. PdI2, 35 2 of 1,2_dihydrofulvene with Na2PdC14 gtves (80).

Cl

Me3c

'.. a3c:-

N

.'

._

_..

. . . ..

473 which gives

(81)

by treating

PdCQ(PhCN)2 with Me3CWH 12021.

with ally1

on treatment

chloride

oxidation

reaction

bridging

are considered

to Qslladium

halide

nm and 245 nm respectively The crystal

structure

norbornyl)NitIt) (-)-*-NiBr

acid

is described

{204].

The charge

transfer

(+)-(fl-R)2NI

(82)

IX.

with ally1 of

Delocalized

entering

ta complexes

(C4Me4B2P2)Ni(C0)2

Ni-tG(l

[206].

respectively vith

(-I-

by a p\hotochamical

Ni(l,S-COD)2.

been prepared

The compounlts

from (+) and I-)--of

The authors

the inter-

report

the

nickel?cene

to give

[C5?15NiC5H6]+,

electraphilic

than at the metal,

attack

leading

occurs

to the

an -exa-methylene position 12091. The single a ring opened retraphenylcyclobutenyl palladium

of

Mechanistic

reaction of

type (83)

The molecular f212].

prrsngement

pathways are discussed

between nickelocene [Zlll.

displaces

to have a sandwich structure

resemble

with dirtanceu

A

sulEides

CO from Ni(CO)4 to give A single structure

and spectroscopic

tboaa of the laaelecttonir

An electron

(2101.

and phosphine

l,h-DIfluoro-2,3,5,6-tetramethyl-

and (C,,14e4B2F2)2Ni (84).

shows it

coarplexes closely duroquimmc

[PdX(C3H5)]2

223

Compounds (+)-F-RN~NIXand

compound [ZOSI.

rather

-1,4-diboracyclohexa-2,5-diene

*

ha-e

protonates

ligands

reduction-complexation

ayWSry

[207].

arti used to show that

complex has been reported.

Compound (64)

of

found at

occupying

cryataL structure

leads

of

systems

acid

experiments

proton

effects

transition and is

YgBr, with disproportlonntion

nickel

carbocyclic

at one of the ring

Steric

(82).

Trifluoroacetic Deuteration

(“-C3H5)

palladium

X * Cl, Br, E) have been prepared.from

and (-)-(n-R)2Ni

structure

band,

for the Cl and Br complexes

mediate n-allyl-a-pinene crystal

is a characteristic

with PX3 and reaction

RNiBr respectively

NICl(CNR)

12051,

and (+)-(iR,SR)-n-pinene

reaction

gives

Ni(1,5-COD)2

n-allylic

has been solved

(lS,SS)-H-pinene

But)

be prepared

of di-~-trifluoroacetato-bis[2-(methylallyl*3-

(R = pinenyl;

oxidation

Treating

of steroidal

compounds with 3-chlorobanzaic this

Complex (YO) can also

and RNC (R = He, Et,

The regiospecific

12031.

with HCL.

QlffractiUn of 2.l28(5)

study

crystal

compounds

study

with idealized properties cooplexes QE cQNiy

and 1.58(L)

of

of D2d the

of

ahoo;r t linear A reSpecr;ivelY

for

the

Xi-C

and

Ni-12: distances

leads

structure dienyl

of Ligands

dimethylallrne

oo adjacent cpPdBr(PPr3i)

to

a d’mer

(84)

sh(avs

it

groups

with

to have

both

the

is

QF. in TW

structure:

dienyl

tith

coordinated gives

stoichiometric The crystal

2-methylallyl

to

and

structure

shows

that

platinum

cyclo-

the

(2151.

cvclopcntaof

L,l-

olefin

(2161.

bridged Use of

with

Treating

a compourd IA-cp-U. 3rPd2(PPr3i)2,

shows the palladiums

unec;ual C-C bonds

1214).

The crystal

positions.

(?-methylallyl)

in exactly

(85)

*iphenylphosphine)platin~n

bis(t

methyl

Ph)

cpPd2(C4H,)(PR3)2

in br ‘dging

the crystal ring

React I on of

and PR3 (R= OMc, OPh,

pentadienylpalladirr amounts

[213].

where

bg’ Br and a cmlopentathe shift

reagent

415

c3l

cs

CY

C(5)

Eu(fodI3

has been

rotational

barriers

cpNiCN(PPh3).

used

to provide

for complexes

For the nickel

C(4)

evidence

for preferred

cpFeCOCN(PPh2Me).

compound

the phenyl

cpFeCOCN(PPhMe2),

multiplet

to -65OC. Effects of Eu(fod)3 on the aromatic protons 119 Sn Hassbauer spectra are reported for eleven Sn-NI Cl~Sn[NiL~pl~_~ molecule).

For compounds

and the SWNi poorer

X.

donor

Metal

acceptor

with

remains

is reported complexes

and and

sharp [217].

of type

x = 2.3) and Cl SnNiL cps (S = solvent 2 3 an Sn-Ni bond, cpNi(PPh3) is the best donor

bond has the highest

s-character.

and the So-Ni bond has smaller

CpNi
is a slightly

s-character.[218].

hydrides.

A series tabulated

(L = CO. PPh3;

conformations

data

of complexes for.LJ(Pt-ii)

strengths

trans-PtH(PEt3)2CN+L

have been prepared.

can be used as a measure

of the Lewis

acids

CL>-

The

of the relative

Coordination

of the cyanide

to

478

Reaction

of pt(PEt313,

pt(pMe3)2(trans-stilbene).

Ni(PEt3)2(1.5-COD).

COD)2.

the closo-metallocarboranes PMe3.

pMe2ph;

complex graphy

(94) from Pt(PNe2Ph)& These

Pt(PMe,Phj4,

authors

Ni(1,5-

close-2.3~Ne2-2.3-C

l,l-L2-2,4-Me2-1.2.4-MC2BgNg

H = Nip L2 = 1,5-COD,

[233].

with

Pd(ChXuf)2

B H gives 299 (M = pt. L = pEt3.

L = PEt3; M = Pd, L = ButNC)-

has been

investigated

also report

by x-ray

the reaction

The

crystallo-

of Ni(COD)(ButNC)2?

and Pt(PEt 2-NXe3-2-CBlOHzo

) (trans-stilbene) vith [close-CBIOHI1land a32to give the close-metallocarboranes [1,1~2-1.2-MCB~~H~~~~

and l,l-L2-2-N?k3-l,2->ICBIOHIO

(H = NT, Pd; L 5 ButNC;

M = Pt, t = PEt3).

_

479 A

single

crystal

structure

Ni(1,5-COD)(PEt3)2 Analogous

with

reactions

betveen

Ni(C2B,H9Me,)(PMe3)2,

the metal

Reaction

Pt(PPh3)2(srilbene)

Pt(C2B7HgEIe2)(PEt3)2.

bonded

12341.

of

with

Pt(C2BiHgPle2)(P?le3)2

[6,6-(PEt,),-5,9-Xe2-6.5,9-NiC,B7Hgl

to a B2C system

of --2,4-C2B5H7

in a 1,2.3-n

bonding

mode

gives

closo-

Pt(PEt3)2(styrene)

H _ Reacting Pt
treatment

with

activated

CPtCB8H10.

E-ray

XII.

isocyanides

Metal

Binuclear prepared ligands chloro

charcoal

structures

complexes

vith

causes

bridge

complex

isocyanides

with methanol

The Pt(IV)

compounds.

But) are also

reported

IPt(CNPh)211Pt(CN)41 derivative

[2391_

[2381.

has been Treating

I_

b

Ewid&ce

is presented

(ChR)2(PMe2Ph)2] are obtained

on

12361.

have

been

the dimers

from treating

chemistry

with

with donor the tri-

platinum

PtCl,(ChX)(PMe2Ph). 51

(R = Xe, But, Cy, p-

by addition

of Cl2 to the Pr(II1

[PtC12(CN)(CNR)(P?!e2Ph)21f

An interesting reported

fluorescent

along with vith

the ButNC

(R =

compound

INi(CN)412gives

Pt
oruonr-fPd(RSC)LCl.1

I 1-p-ro’“idinc

for analogous These

and

Pt(C2H4)(PPh3)2

PL-[Pd(RYCXCH,,SC,C,

l+oC~Ii,, F-ClC,H~)_~

result

PtC14(CBR)

PtC12(CN)2(CNR)2

are given

Treating

A similar

[237].

compleres

1,6-C2B8Q,

which

(R = Ph, E-NeC6H4)

Carbenes

to prepare

[PtC12

Complexes

compounds

and PdC12(H&2.

has been used

[PtC13(CX0(PXe2Ph)2]~. tolyl)-

of all three

splitting.

[&I.

gives e-8,8-[(P?le3)21-7.8.10-

[PdCl,(CNR)J.,

from PdC12(CNR)2

of

) _

Pt(zE: ) 32 respectively

gives

2,3jPEt3]2-l,2,3.6-CPt~CB gives

Reaction

Ni(C2B7HgX2)(PEt

‘

Astructure

.Pt(C2B7Hll)(PEt3)2-

is given gives

C2B,HllNe.Ie,and Ni(l.5-COD)(PHe3)2,

Pt
(stilbene),

shovs

of the Pd complex

5,9-He2-5,9-C2B7Hll

compounds

AL-[Pd(C(NHR,SHcr,ltrlc)(CH,*SC)Cl:)

compounds.with .&d-I,,

UeI,

RXC (B = Pri, CY. ECF_I,

SnClPh,.

Treating

480 with

'c(C~F~)<~P~~)~ compound Careful

PtI2(CNMe)2 synthetic

vork

(Pt(CNR1411Pt(CN)41 reacts with The reaction PdC12

gives

presence

CNR'

RNC

(R = But. Pri)

is obtained leads

to compounds

Pt(CNR)2(C2F4je

(R' = But, R- clc6R4)

and Me1

IPt(CNR)2(CNR')2l[Pt(CN)41

t0

of a large

carbonylpalladium(I1)

2PhN=PPh3

f

isocyanide excess

palladium(I1)

of CO, complex

compound

PdC12

12431.

and

12421.

[Ni(CNR')2(S2CNR2)]+

give

of CO and triphenyl(phenylimino)phosphorane a phenyl

The (240).

[Ni(S2CNR2131~ (R = Et, Bun)

The compound

[2411-

gives

from Pt(CN)2(PPh3)2

complex

in the presence

(95) is converted

A dark

of

(95). In the

red cluster

into a compound

-I- CO -

I (PhN=PPh3)PdC12(CO)

A

(PhN=PPh3)PdC12(CNPh) (95j

Ni4(CNBut), spectrum energy

has been

shous

prepared

stereochemical

step being

from Ni(l,%COD)2 nonrigidity

one involving

(96) has been solved

(2441.

the bridging

Acyl

and ButNC.

by a two-step

chlorides

ligands. or phosgene

The%inmr process, the lower

The structure have been

of

used

481 to convert

the cprbonyl

Electronic

12451.

compound

absorption

and FUZD spectra

He, Et; N = Pd, R = Et) shows the visible

or W

region.

(97) into the isocyanide

intense

Spectral

assignments

BRR

NEt3

i Cl

(97)

distance-

XIII.

(98)

are discussed

from treating

structure

(2461.

Na2PdC14

dependent.

is the shortest

The angle

The compound with

The crystal

about

reactions

[249]

-

-A ee

used

(99)

structure

shows

distance

a Pd-Pd

is

distance

for this bond

i for the O-O

the N of Bu?iC

5s 172<1)O

12481.

involvinn

The

complexes polystyrenes

for the hoaogeneoua

to aniline

of

[247].

of 1.45(l)

of Pt
sioa of nitr?benzene

[Pd2(CNKe)6](PP6)2

The 1H nmr spectrum

a value

Diphenylphosphino-functionslized .or PtC12 have been

KeNC.

recorded

shows

of Ni<02)
Catalytic

participation

Cl-Pt-CNR

Cl

2.531 i. vhich

and d orbital

in

I

CCJClz

Ph3P-Pt-C' -0 I

temperature

transitions

PPh3

I

results

(98)

of M(IZNR)~~~ (M = Pt, R =

N * L charge-transfer

PPh3

in bonding

compound

and pyridipe in 90% yield

coordinated

hydrogenation

with

PdC12

of monoalkenes

has bean used for the conver[250].

+nd.lys@

The complex

for the hydroformylation

of

482 greater and

than 95% yield

it

is reported

heterogeneous

Naphthalene

final product.

with

both

12531.

This

RC(Me,)CR=CE2

latter

exclusively

PBu3.

regiospecific

Bu%C,

Fxchange

PButPr2,

in the order:

PPh3),

PdC1L(PPh3)

reinvestigated.

compounds

are also

h mechanism

Steric

with

undergo with

> 4-membered

by PdC12L2

Pt2C14L2 a

deuterium

PButPh

factors

are considered formation

12561.

(L = PhCN.

[PdCl(r-C3H5)1,,

The

CySC, has been

the

formed:

i-trimethyl-

4-trimethylsilyl-l-butene,

l-trimethylsilyl-1,3-butadiene,

n-allyls

catalyst. occurs

to 1-trimethylsilyl-2.6-octadiene,

The analogous

involving

[254]. a

Complexes

PButPh21

however

and

study

form

of Pt, the ease of ring

Bu'NC),

to be

is also observed,

[255).

to give complexes

> &membered

give

with

Pt(IE)

hydrogens

PPr2Ph,

catalyzed

(L = CyNC.

In addition

silyl-trans-2-butene. silylI-2-butene.

5-membered butadiene

H-D exchange

reaction

in the aryl group.

the

exchange

comparative

in communication

phosphine,

metallation

s-D4 being

part of the alkene

PPrPh,,

and

anthracene,

m- and P-terphenyl

and a homogeneous

in D20/CH3C02D

and in internal

of .Xe3SiH vith

following

FBu=?Pr,

with

prolonged

A similar

of the olefinic

of the tertiary

is incorporated

decreases

HClO&

Na2PtC14,

type are suggested

diphenyl.

to be an acid-catalyzed

groups

be dominant,

12521. with

into the alkyl

H-D exchange

in the alkyl

reaction

containing

at C(5).

(L = PPr3,

Pt does

is also published

of deuterium

and is considered

B-orientation


solvent

Incorporation

deuterium

work

Homogeneous

of the n-bonded

types of catalyst

Alkenes

D,0/CH3CQ2D

initially

by these same authors

is uncertain,

in D20 of naphthalene,

the heterogeneous

Intermediates

has been made

of the complex

unstable.

the exchange

yields

only with

naphthalene-D8_

The structure

to be relatively

Pt, catalyze

and pyreme_

involved

[2X].

reaction

with

is suggested

Me3SiD

[257].

1.4-bis(trimethylhas been carried he

major

products

out. from

to

the hpdrosilylatian of butadlene with C13SiH are butene and 1-trichloroailyl-trans-2-butene. Nix&

1-trichlotosilyl-cis_2-

The catalysts used are of type

(X = F, Cl, I, N03, !4eC(-O)=CHC(=O)Me,neCH(OH)COO;

PBu;, PCy3, P(OPhI3,

AsPhj;

L2 9 DPE).

Similar

L = PPh3.

allylnickel Intermediates

arc postulated [258].

HydrosilyLation of HOCH2CH,CH=C=CH, with Et35iH in * the presence of M,PtC16 gives 1~OCH2CH2CHICHCft2SSEt3.Similar catalyzed

ndditons

are

addition

to

_ reported

Me3SiH

Again further

uses

Acetylenes Iw catalyzed of

group

p-MeO,

p-Cl,

of

compounds

[Lb?].

p-k,

to give the

the

of

silanes

A variety to

the

_

double

SC6HhCOCI (X = ti,E-He. _q-MeO, into

XC,,H4CH0by treat-

aldehydes

Ni (COD)2

HSIX;

an initL.Il

Et+H

20°C

of

oxidat

.

PtCl,L,

!

occurs [261).

addition

c

trans-LH3CH=CHCH

2

OS iX

3

rxt)

One,

involves

The reaction

Addition across the carbon-carbon halides

dr‘~ covet-ted

+

silyl-olefins,

silylation

at 120°C in the presence

Et3SiH scheme

camlvzes

~~~-trimethylailyl-i-~~lt~rlt~(260].

catalyze

A
p-NO23

(S f

proposed

Ni(acac)2-Et3AL

give

crotono?dehyde.

occur

trans-CH3CH=CHCW1, _-

ment with

to


nickel

bond dots not

The systtm

bueadiene

add HSiC13 or HSiCl,?le L by NiEt2
zerovalcnt

carbonyl

[259/. to

c&-PtC1,(PPhY)2. c

iw

addit

ran

rz631*

The

A product

PtHCl,(S.Et~~L,

-Ft+CI

-WHO I

RLlx.1

PtHC12(CDK)L2

PtHCLL2

*

( L = PPhJ distribution

Is reported

for

the catalyzed

isomerization

of homocubane.

Compounds used are PtCIL,

PdCL2fFhCN)2, PdC12
These authors

a similar

also

report

cubane rearrangement

to oligomerize

resin-anchored butadlene

COC. Anchored IrCI(CO)(PPh3)2 to cyclooctene gives [267].

12661.

a 95% yield

The chloro

1,8-bfshomo-

f265].

Polystyrene-dlvinylbenzene selectively

study on the catalyzed

[264].

The catalytic

of one specific analog

givta

to either

catalyzes

Ni(C0)2(PPh3)2 4-vinylcyclohexene

the hydrogenation

system NiBr2(PFh3)2 linear

product

only 81X yeild.

of

has been used or 1.51,5-COD

mired with KaBH4

(E,E)-1,3,6-octatrie~e The polymer bound analog

484 of the bromo

compound

gives

and free Ni(C0)2(PPh3)2 vinylcyclohexene,

shows

that butadiene

1,5-cyclooctadiene

catalyst

are hydrogenated

used

catalyzes

pseudo-norbornene. of this product addition

to a third molecule

product

facilitated facility

12701.

by ligands

L vhich

in relation

compounds

12711.

Complexes

tNix(PC~3)~l~

or Ni(Pc~3)3.

PBu;. PEt2Ph)

to compounds

N2 to give Ni(N2)L3. discussed

Electronic

for these compounds

1698
[273].

Ligands being

A series

L cover

favored

_

-

phosphine

_

-: _-

+

.-.

Cs2(g)

;--

: _

yields

compounds

NI(PCy3)3

react with and

or [NI(PCY~)~]~N~

spectrum

are assigned

shows bands

to vibrations

of compound

at

of

(100) is

(n = 2, 3, 4) have been prepared. the lower ligand

coordination

(e.g. PBu>h).

a bond angle

-+

is

and similar

are presented

by 13C amr spectroscopy

shows

This

geometries

sodium

These spectra

structure

of phosphines.

of Pt(PCy3)2

Pt(C2E4)(PPh3)2(cryst.)

_-

cm-l, vhich

PdLo

is likely

(X = Cl, Br; L = PF3.

The infrared

has been studied

structure

NiX2L2

crystal

the addition

interest

(100).

of complexes range

of these

Treating

single

to a dimeric vith

NiX2L2

(X = Cl, Br) with

absorption

by the more bulky

tion equilibria crystal

a wide

The

these

anchored

properties.

12721.

and 1150(s)

CO,.

the coordinated

actiivty

of general

Similarly

when

to give a trimeric

and square

NIL4 are obtained.

with CO2 gives Ni(C0)2(PCy3)2 174O(vs).

a-acceptor

tetrahedral

of NiX2
to 4-

The complex

is involved

of complexes

to the catalytic

and reactions

The reduction

12691.

of norbornadiene

possess

betveen

process

of norbornadiene

further

Isomerization

of isomerization

discussed

XIV.

from butadiene

then

on anchored

can be cyclooligomerired

on the same polymer

the cycloaddition

The catalyst

vork

(E,E,L)-1,5,9-cyclododecatriene

to a multistep

to alkane

for their synthesis

Ni(C0)2(PPh3)2

shnwn

and

This work has been extended

f2681.

three dienes

Further

91% of the product.

[274].

of 160.5*

.-..

The

for PPtP

Pt(cs2)
number Dissocia-

T

12751.

c2Hqw . -._

485 disulfide

has a AH of -44.0 + 2.2 id mol.-1.

D(Pt-CS2)

is slightly

measured

greater

The bond dissociation

than D(Pt-C2H4)

[276].

Enthalpies

energy have been

for the reactions:

i- nCS2

PtL2

*

PtL2(CS2)

+


PtL2(01efin)

+

CS2

This data. when

combined

of the Pt-olefin

bonds

+

vith

previous

decreases

e-1.2-diphenylethylene

+

olefin

uork,

shows

in the order

s phenylethylene

(M = Pd,

X12(Ph2CXCF3)2

PtL2(CS2)

the relative

3 ethylene

Pt) uith HCl yields

strengths

trans-1.2-diphenylethylene [277].

>

Treating

-cistrans-PdC12(Ph2PCH=C(Cl)CF3)2

and -cis-PtC12(Ph2PCH=C (C1)CF3)2 by trans addition to the triple bonds. The structure of the palladium compounds confirms the stereochemistry about the double

bond

12781.

Treating

Pt(HC~Ph)(PPh3)2

Pt
The crystal

to have a trans

about

bonded

configuration

diazene

complexes

of nickel

Ni
exhibits

from bis(R-methylbenzoyl)diazene structure crowding Wen

within

ketoximes

molecular

the molecule are heated

oxygen,

leads

of the product

[279].

A series

The compound exhibits

a N-N distance

it

of a-

obtained

fluxionalicy.

of l-238(9)

to a twisting

of the phenyl

in the presence

of Pd(PPh3)4

fragmentation

gives shows

12801. The compound

have been prepared photochromism.

shows

at 60°C

a Beckman

the N=N bond

vith nickel(O)

of PdC12(azobenzene)2

with R-FC6H4N2BF4

structure

of the ketoxime

i.

rings

The Steric 1281]_

and

occurs

to give a

nitrile

and an aldehyde

12821.

phenone

hydrazone

is treated with py, PR3
(101)

=Ph3,

the monomers

second

molecule

an ionic complex

are formed.

coordinates is formed,

When

the cyclopalladated

In the presence

of excess

in place

of the nitrogen.

and with

DPE a dimer

X

dimer

of aceto-

phosphine

With

is obtained

a

ethylenediamine with

the DPE

=

Cl, Br. I

R - H. Me, Ph 2
molecule bridging.tw palladiums have been

12831.

The compounds

NIL2 and NiL(PPh3)2

obtained by treating Ni
Similarly Ni(C2Fih)(PPh_,)2 _~.$'-b_~(~tb~lpbe~hplpaenJrT)etb=lenedi8ine(L).

486 reacts with PhCH=hiPh to give Ni
12841.

of Ni(O), Li[NiPPh2]2THF,

Li,[Ni
and Li31JJiiSiPh3)3].

5THF are reported

The binuclear

trinuclear

[2SSl.

in benzene

by refluxfng

Pt(PPh3)&

atmosphere_

The verification

[286]. XL4

Paramagnetic

(L = PEt3*

cyanoethylene. observed AsPh3.

the %I-

[287].

P
species

Pt2
(103) cluster

P&j(PPh2)3Ph(PPhg)2

compounds

for several

have been observed

comes

electron

The initial

paramagnetic

PdX(Bu~NO)L

have been prepared.

and infrared

data

acceptors

The nitroxide

for the compounds

by treating

as tecra-

are not

is "side-on"

is-reported

.

are prePa+

such

species

study

compounds


crystal structures of cortpotmds(104) a&(105)-haye ComPo=ds

a X2 or Ar

from an X-ray

on treating

PPh 3.- L-L = DPE) with transient

(102) and

have been obtained

days under

of the structure

The compounds

The compounds

c~~.,pt.N(B)N~_~<~?L2

bonded

I2881-

The

been solved_. The

I

_<&

and

_--

Eh, E-_ ~_ :

.__~

small

amounts

of hydrate

(CF3)2C(OH)2

The liquid

[289!.

phase

oxidation

of

/CF3 =\ ,'-'+CF L,pt\_C&F;

L = PPh3

(104), P?fePh2 (105)

\CF3 benxaldehyde products

is catalyzed

are benzoic

resembles

by Pd02(PPh3)2,

triphenylphosphine-in

intermediate but work

Pd(PPh3)4.

acid and perbenzoic

of type

markedly

retarding

(106) is considered

by us [291] on the oxidation

PtO,(PPh3)2.

The latter

acid.

the reaction

to be a possible

of ketones

Ihe

compound dn

[290].

intermediate,

by these complexes

o-c PPh3)2Pt'

\C,H , -Ph

. ‘0’

(106) concludes vibrations

have been

observed

m = l-3). and are assigned compound

Pt(N2)'

of the vibrational

at 6-lOoK spectra

labelllng

[293].

"End-on"

observed.

Mixed

halocyano

(PPh3)4

+

XCN

Condensation

gives

and Pt(X2)m


are made with bonded

Pd and Pt atoms vith

of Yi -,

compounds

?f(O2)x(K2)v.

the assistance and "side-on"

nitrogen

complexes

-

Pd(X2)m

for Ni(X,)n,

Lou frequency

stretching modes. The -1 of v,~ at 2197.6 cm , and for the asymmetric

has a value

02* K2* Ar mixtures

is operative.

to metal-nitrogen

at 360 cm -1 [292].

Pt-N stretch

Pt

chain mechanism

that a free-radical

(107) have been

Ihe assignments

of isotopic bonded

prepared

oxygen

are

by the

(X = Cl, Br, I)

PtX
oxfdative

addition

replacement halide

[2951-

Infrared

(X) (C12, Br2, The conditions

compounds excess

cyanogen

halides

of X by X3, NCO. NCS,

compounds.

halogens

of

which

Under

is reported.

is stable

to air.

that tvo isomers

Pd_C02C6C14)(PPh3)2

An analysis

of the

The complex

any free triphenylphosphine. is a white

of the 1' F nmr spectrum

exist


trans-PtX2(PPh3)2

isomeriration

bis[l.2-bis
concluded

[296].

A crystal

the quinone

pseudo-

conditions

This can be done by using

does not occur. with

suitable

to give

are such that subsequent

reacts

Metathetical

[294].

to the corresponding

12) add to Pt(PPh3)4

to the cis isomer

halogen

data

to Pt(PPh3)4

ch.0 leads

chelated

powder

of the complex

structure to the

which has

of

metal through

488 CL4

(708) oxygen

donors.

Bonding

with a hydroquinone orbital

treatment

appeared

which

parameters

electronic

of pentacoordination

is of general

organomecallics

withfn

structure

the quinone [297]_

in transition

interest

ligand

are consistent

A unified-molecular metal

to any workers

compounds

in transition

has

metal

[298].

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