The crystal structure of o -(diphenylphosphino) phenyl-cis -1,2-dicarbomethoxyethenyltriphenylphosphineplatinum.

121

Journal Of OgonometaXltc Cclemisby, 145 (1978) 121-138 8 Else* +quoia SAY.. Lausanne -PrintedinThe Netherlands

The

Crystal

Structure

of =-(Diphenylphosphino)phenyl-e-1,2-

dicarbomethoxyethenyltriphenylphosphineplat%num.

Nicholas Department West Texas

Rice

C.

of Chemistry and State University,

The

structure

Joel

D.

*

Oliver

the Killgore Research Texas 79016 Canyon,

(Received

ea&y

and

Play 31st,

Center, (U.S.A.)

1977)

of o_-(diphenylphosphino)phenyl-cis-

l,Z-dicarbomethoxyethenyltriphenylphosphineplatinum, [Ph,P(C,H4)]Pt-e-(C02MeC=CHC02Me), single

crystal

X-ray

has

diffraction

been

methods.

space

dimensions

2 =12.560(l),

b =

13.600(l),

1'0.01(1),

6 =

and

y = 91.03(l)'.

density

of

consistent

g cm

with

the

coordination the

tvo

about

phosphine

another,

The

chemistry. in and is

this

97.58(l),

1.57

-3

for

the

the

compared

to

2.330(2)

the

;;.

These

and

2.026(B)

the

trans-influence.

yielded

bond

(0.048

whose

intensities

> 10 -

counts

s

-1

).

for

those

per

cell

respect

The with

to cis

one stereo-

metallocyclic

ring

metallocyclobutene

average

Pt-P

bond

lengths

are

discussed

R)

cz=

is

g cm -3 .

least-squares

weighted

with

calculated

possesses

of

The

lengths

are

with

four-atom

Pt-C

Full-matrix

R = 0.047

flections (I net

observed

A

are

i,

square-planar

also

complexes.

i and

is

cis

group

of

platinacyclobutane

atom

cell

11.452(l)

1.56(Z)

by

crystals

unit

units

of

oriented

vinyl

geometry is

value

per c =

formula

platinum

ligands

compound

molecules

two

measured

o-bonded

The

two

PY,

determined

The

triclinic,

group

(Ph3P)-

based

significantly

bond

are

length

2.059(g)

in

terms

refinement on above

the

5208

of has re-

background

-..

During-

an

the- the&al.

examinatioh-of

stability

bf

carbomethoxyacetylenebis
Rine

.[l] isolated

a-product

formulated

diClark

as _.

COOCH3 I resulting chemical NMR

from

assignment

The

metalation. I was

for

based

detailed

upon

the

stereo-

observed

IR

and

spectra. Although

have

been

action via

metalation

known

for

yielding

reactions

some

I is

as

H2*

the

the

by part

an

reaction

Pt-H

of

elimination of

time

alkane,

forming

the or

I,

bond

subsequent

Molecular

structure

aryl

as

the

mechanism

bond

resultant part

metal

reactions

C-H

insertion

to

transition the

These

an

of

of

12-41,

unusual.

oxidative-addition

folloved

In

internal

to

a more

of

the

of

the

normally the

hydride

of

complexes

oxidative-addition

atom

the

complex

alkyne

proceed

metal in

re-

form

of

species.

ligand step

into is

required.

have

predominantly

atom

chelate

structures riugs the

tvo

analogous identity

involved Perego

rings. of

of

studies

to

iridium that

I and

to

of

complexes and

containing

coworkers

complexes propcsed allow

orthometalation

for an

I.

five-

[5,6]

containing In

unambiguous

products

have

or

six-

reported

four-atom

order

to

confirm

assignment

of

123 the

stereochemistry

diffraction

A

sample

of

of

H.

ethanol

data

C.

and

crystal

the

the

molecule,

investigation

Professor of

of

the

title

Clark

and

orienter

using

Cu

Kc

kindly

before

11211

studies

diffractometer

was

X-ray

supplied

recrystallized

with

X-ray

goniometer, 700

compound

chloride

mounted

crystal

initiated.

was

methylene

was

Diana-XRD

was

a single

were

at

a 2:1

The

use-

parallel

to

with

room

phi

axis

using

a single

ambient

mixture

colorless

the

performed

equipped

radiation

from

by

a

crystal

temperature

(~~21°C). intensity vealed

only

symmetry

weighted

triclinic

was

listed

refinement

of

well

66

the

by

in

symmetry

a reduced

Table

cell

1 were

independent

reciprocal

lattice

(?a..

No

higher Lattice

calculation.

obtained

by

re-

least-squares

reflections

with

Ka

the

was

determined

and

O.OS"

1

and

Ka

2

resolved. The

mosaic

inspection slit)

of

for

suitable

0 scans

of

USiQg

crystal

for

data

were

sities

noted

were

.5"

the

Ross

off

thus

no

angle

The

scans

and

revealed


take

filters. and Only

angle

During

data

correction

for

that

indicating

and

of

variations crystal

1"

receiving

collection

intensities

random

receiving

stationary-counter

off

the

by

peaks

symmetrical,

stationary-crystal,

aligned

monitored.

crystal

wide),

collection

frequently

reflections

take


(<

balanced

was

of

reflections.

narrow

quality

technique Slit)

character

several

were.single,

was

of

diffraction

revealed

parameters

plots

the

6 standard

in

inten-

decomposition

required. The

of

crystal

to

4.97.

intensities shape

were

[7] with

Additional

corrected correction

corrections

for

for

absorption

as

factors

ranging

Lorentz

aad

a function from

2.86

polarization

Crystal

Data

861-79

'

for

WT. . .

C42HB604P2Pt

_. Formula

_.

Weight

‘_L

Triclinic

.

.:.

.

Sk = 12,560(l)

;;-

& = .1;.600(1) .: , c’11.452(l)

;;

Spaces-group

;;

Z=2

Systematic

.

a = 110.~Ol'{()'

PCOOO)

S = 57_.58&

x cu : Kal,

y = 91.03(1)0d d

= 1.57

calcd

pi

3 856

Ka2, g cm

.. measd- = 1.56(Z)
none

absences:

I

.

‘it>

(NO.

e

1.54051

;;;

1.54433

;;

-3

_ .

g cm

-3

aqueous

. AgH03)

_ . Crystal u(CuK;) 5390

Dimensions: = -85,33.-&x

syvkietry -. <5208

Data

*0.09

Collection x 0.10

x 0.14

mm

-1 for

independent-reflections

reflectfons

3zitII Inet

6°-~26

counts

110

5

120°.

s-l)

_.

.

_..

effects, Standard and for al-a 2 splitting 181 were applied. . deviations in the observed structure factor amplitude&, u
map.

determined A

posit&on8 The

five

by

subsequent of

all

interpretatfon electron

remaining

noumetalated-phenyl '. _..

of

density

a three-dimensional calculation

rings

revealed

_

nonhydrogen were

atons

Patterson

.

of

treated

-

the

.:

the

structure,

.__

.

as

__...

rigid

-. .--

groups

125 :-with idealized

geometry

C-Rdistances each

0.95

carbon

-atom

was

ti = u

where

R2

=

calculated

structure.

model

and

nonhydrogen, parameters thermal

the

with

hydrogen

refinement

for

the

non-group

parameters to

O-048.*

A.final

a number

of

peaks

of

the the

complete difference in

the

the

leastelectron

peaks

in atoms

included their

rea-

in

of

all

idealized

least-squares

refine-

overall

scale

an

(6.1<5)

x.~O-~

six rigid

refinement

e-2)[10], of

orientational groups,

and

atoms at

Rl

1.0

e i-

the

and the of

the

map 3.

in

the

nineteen

positional

isotropic

= 0.047

electron-density of

factor,

parameters

nonhydrogen

order

.096,

hydrogen

were at

thermal

atoms,

of

eleven

Additional

parameter

in

contained

atoms

the

=

A difference

calcqlations

anisotropic

and

.057

minimized

remaining

varying

each

=.

point

hydrogen

nongroup for

served

each

12)/P~<1Fo[)21'

this

02 6..0 A _

B.=

positional

*

for

extinction

isotropic

of

&I(~F~I-/F~I)~.

least-squares

this

1.397

temperature

Least-squares

function

at

These

positions.with

rings

The was

positions

of

factor

i/S IF,/

[='llFoI-IFcl

-2i1F&

map

ment

distances

isotropic

factors

temperature

= TiIFoi-/Fc-i

density

subsequent

C-C

least-squarescalculations,

temperature

R1

calculation

the

angl'es,

at

squares

.sonable

the

to.6.'0 I;'.

isotropic

converged

bond

-ti variable

isotropic

constrained

employing atoms

_i) in

atom-assigned

The

factor.

(120*

phenyl -and R2

=

contained

the

vicinity

.The table of.structure factors has been deposited as NAPS Document No. 03157 (26.pages). Order from ASIS/NAPS, c/o Microfiche Publications, P-0. Box 3513, Grand Central Station, Nev York. N.Y. 10017. A copy may be secured by citing the document number, remitting $6.50 for photocopies or $3.00 for microfiche, Make checks payable Advance payment is required_ to Microfiche Publications.

i,

._

_~ _

. _.

Y

z U(l,l)

U(2,2)

U(3,3)

262(61) - 19(53) 622(66) 652(66) 1080(90)

3319(7) 2764(a)

4203(7) 4685(a)

3621(7) 3191(7) 3702(a) 4679(g)

1624(5) 3293(5) 2074(6) 925(7)

2468(a)

2021(6) 2138(6) 1909(a) 1532(a)

- 137(5)

113(6)

1823(6)

1458(6)

1443(9) - 670(g) 2729(7)

1774(S)

1327(6)

366(7)

- 837(U)

4221(6)

5182(6)

6178(7)

6183(a)

o(2)

O(3)

o(4)

C(1)

C(2)

C(3)

c(4)

C(5)

C(6)

C(7)

C(8)

c(9)

CClO)

_

139(50) 495(55)

884(75)

4319(6) 5620(7) lO79(58)

'522(55)

3553(6)

431(5)

607(59)

416(46)

2(43)

22(38)

l21(44)

36(37)

645(66)

680(62)

- 17(43) 494(56) - 71(52)

437(49)

131(39)

744(82) 1605(122) -108(70) -340(86)

581(59)

444(49)

709(48)

362(42)

- 72(35) -132(38)

884(53) -271(42)

897 (49)

510(39) -172(36) - 80(35j

686(49) 1051(58) - 13(42)

757(51)

560(42)

671(45)

,’

18Oj45)

744(86)

320(50)

214;(40)"

.70(43)

67(42)

4&i(39).

,.

183(34j

116(g)

;18i(lO)

.‘.

r, I 6:

-.

397(44)

551(51)

-

535(53)

390(47)

-

356(44)

319(42)

..

126(,38)

43(39)

-

-

9(43)

39C35)

3(37)

369C64)

241(?3),.

'llOC3?)

,,

',23(36) ,, ,q

194(47) ..lOj.(50) ,; ,' 3111(10) 6134(14) 1747(138) 1055(109) 2114(159) 192(96) 161C(l28) '255005).

661(62)

439(48)

3069(12) 1135(97)

471(50)

445(45)

920(53)

847(47)

892(40)

70(8)

1719(5)

31(9)

500(5)

352(U)

992(T)

405(12)

o(1)

347(10)

1958(2)

59(9)

2635(2)

IA(g)

4726(l)

414(12)

P(2)

446(12)

ll49(2) 354(11)

,’

U(>,3)

,. ‘,

696(13) 1257(15)

U(1,3)

2992(2)

300(13)

U(l,2)

1836(2)

30325(3) 24536(3) 25098(3) 3262(21) 3501(22) 3428(21)

X’

Atoms of C,,2H3604P2Pt .’

Fractional Atomic Coordinates and Tharmal.Parameter6 (x10') for the,Nongroup

P(l)

Ptb

.xw-n#

Table 2'.

7019 6020

- 924 3439 2400 3242 3562 1990 1362 1150

1450

1621

-1106

- 643

-1369

6827

6844

5272

3603

in parentheses

H(3C)

H(4)

H(6A)

H(6B)

H(6C)

H(9)

H(l0)

H(l1)

lI(12)

‘Numbers

Positional for

is

the hydrogen

deviations

625 (61)

903(79)

in

435 (50)

423(53)

presented

x 1.

the Pt atom are presented atoms are

for

exp[-ULl(sinO/A)2].

standard

6.00

6.00

6.00

6.00

6.00

6.06

6.00

6.00

6.00

6.00

estimated

parameters

expression

and thermal

factor

parameters

temperature

the

4926

5806

5044

3393

3746

2526

6.00’

709 (60)

875 (75)

the units

146 (48)

247 (62)

of

173(44)

75(51)

261(46)

317 (53)

x lo’,

._.I“___. _-

the last digit. 2 *2 The temperature fnctor expression for the nonhydrogen atoms is exp[-21r2(Ullh a f U k2bh2 + 22 J( J( 2 *2 + 2U12hka b cosy* + 2U13hfia*c*cosP* + 2U23kLb*c*cosu*)i. For the hydrogen atoms the U33R c

‘Thermal

b

5736

-1042

1928

H(3B)

are

4560

- 776

730

M(3A)

1543

4615 (7)

1633 (7)

4252(7)

Cl121 2611

5123(8)

1406(e)

5252(B)

C(11)

_-. .“.^.__

1

I

I

,

?’

:

.: .,,’

Tab10

1377 (6)

*’: 557’(5) : ,_4’32(5)

6392(3)

c(33) ., ,3263(4) c(3ij” 2612(5)

!.:15.1.8(4), 1 581.0’(4)

4781(4) C(36) $75 (4) , ., , i’, ,.:’ I’.,’

I : , ,’

:; 21;22(5)

,?946(4)

‘3020(b)

c(3i)

c(35)

2b46 (5)

“1 ‘4918(4)

’ 2126(4) 1227 (5)

L :‘I

“A lbl(5)

c(31)

4336 (3)

1057(4)

1678(4)

c(4;)”

.*

-1919 (5)

335 (3)

1629 (4)

h7i1(4)

c(41)

1763(S)

-1493 (5)

.,-*,488(4)

.,I2

,,-2924 (4)

O(39)”

2485 (3)

, 2132(4)

y

group 6 ntome’

PIl(2)

- ,,1’

4,9(2)

.:5.1(2)

,5.?(2) 6.0(i)

4’;,7(2)

3.6(2)

‘4.?(2)

5e,_7(2)

,6.1(2)

” .!‘.

H(35) X(36)

li(34)

H(33)

H(32)

Ii(42)

S(41)

ll(40)

H(39)

‘5.6(2)

Ii (38)

4.7(2)

N(1)

Atom

,3,6(2)

(”

c U(i2)

, ,I’

,,,

x

,

2.963(3)

,,

.I.

2,772(3)’ 47

,s,:

-l-673(9)

1,665(?),

,

: “i&g(4~

-1,612(g) .i;sj;i3j:’

1275(6) 8’67,(5:),‘:

2778(7)

3872(T)

3463(5)

1648(6)

1565 (7)

1641(7)

1798(7)

6113 (6) 4385(6)

7091(4)

6342(6)

4615 (6)

817(6)

- 396(3)

197 (6)

2002 (6)

3215 (3)

Y

I_

-

51(7) 76:(‘6)‘;

1428(E)

2679 (7)

2553(6)

18(6)

-2064 (8)

-3752(4)

,’

‘,

‘8:

j’

i ‘; .;‘I

1,

I :I:;# , .,’

‘;::’ “! ;; !;

>:!

I..,

’ ” (’

b,c

-3394(5)

-1348(l)

E

phony1 group II atoms

-1.916(3)

.’

‘:3.116(3)

-1.942(3)

1881(6)

Dcrivod

0,741(9)

0,0.$68(4)

0.1821(4)

!,,

2,668(?,),,

I,#

‘~1..542’(4)

0.2!1.6(5)

I,.‘.

’ ’ O:i425($

’ 2,‘923.(3)

8: ,

I

&121(9)

-

O.GISS(3)

I.

‘, I

-010488(4’j.

,

’ O-1227(5)

688(4)

1768(S)

C(38)

:

JL4335i3)’

0’.2132Y4)

. . . ,‘, :’

” ‘0’.3di;;<4j

,’

c(40) 8 ,.l674 (5),,

1772(4)’ ‘1017 (4)

~(37).

x

Atom

phchyl

0.5067(4).

PH(5)

‘Dorivod

0.5i’63(4)

d.oh’34’(3j

‘A(4)

’ ‘P’li(3) ” ’

&2’12,6(~)~

9!1(2)

,,

Croup ParnrnoCersA

’ 0.‘1772’(4)

3.

y

‘PH(1)’

..LvwI.

:

;’

‘,

:

I.

I ,.

,,

,- .‘!GI E,

..

-_

-.

.-

:Iof--the. pl‘atfnum and the 'phospho‘jcussatoms; :.S‘maller peaks -1 ;-located near tho:five' rigid phenyl -<0,3. to-.0,8 o ;iy3)- v&e groups

the- ieihyl

or neat

S&at&ring factors -for : oxygen atoms uere taken

-and

anomalous

the

rigid

equations

final

atomic

labeling the

atoms Sand

are

for

selected

scheme

atom

attached

to and

molecular The

torted

and

which

is

planes

Zn

plane

the

Waber

carbon, The

~[lL].

platinum

Stewart,

of the

and

the

factors

Davidson,

for

and

five

Table

3.

bond

are

are

atom

Table

rings

4 contains Figure

The

1 presents

the

atom

according

methyl

H(iB),

displayed

2.

treated

is numbered

H(iA),

4 presents

in

indicates

is bonded.

is monomeric

Pt,

geometry C(l),

plane

comparable

in

hydrogen

and

H(iC).

Figures

a stereoscopic

and 3,

to

and

in

the

the

C(4),

and

intersect

to

the

this, structure

other

reveals

about

angle

2 and

view

of

the

netalated

the

PtPB

[IS].

with

and

the

of

and

The

complexes. ring,

Plane

containing angle

favorably

cis-triphenylphosphine four-atom

an

dis-

atom.

plane

form

80.8"

agrees

a slightly

platinum

between

trans-Pt(COOEt)2
of

Table

and

labeled

angles

phenyl

planes.

hydrogen it

given

packing.

P(2),

in

I are

molecule

Each

Figure

by

angle

observed

in

to which

square-planar

P(l),

the

of

C(i)

structure

defined

P(2)

and

Scattering

least-squares

used.

carbon

vith

given

view

3 respectively.

A.

from

phosphorns,

the

1121.

parameters

groups

iengths

the

Croner for

taken

associated

a stereoscopic

to

from

included

atoms- were

parameters

as

platinum,

[13]_

The The

were

atoms

hydrogen

Simpson

the

dispersion..corrections

phosphorus

.-

substituents.

Pt,

80.51°, Pt_C02

P(1)-Ptthe

values

Plane plane

C. of

.

Figure

1.

A stereoscopic the of

viev.of

atom-numbering 3OI

the.mogecule

illk$trdting EHipsoids

.schejne employed.

-_

probability

are

i ::

sho&.

-_ Z

T. , -1

i

_ -

2_056(8j

I/

-I

-

Figure

2.

Bond given place.

..

parentheses

-.

,

.-

:

1.508(13)

-

.-I distan.c_es.'. The- estimated in

_ ; _.

.:..

refers

to

-_

_. standard:d&iation the

last

decimal

.:-:

ANGLES

;

Figure _.

(

3.

.I’

Bond

P2

162.1(2)’

C?

.P,

PI

PIG

-PI

PHi

173.7ca . Id4.3h

Pb!z

Pt

Pt

114. I Gtl

PH4

PZ

CS

107.3(3)

PZ . .

Pt

liz!.3(2)

,

1 _-

angles. ._

given place.

in

_z

I:.

P?

-PK5 i

.-

:

SHOWN

: cl_

._ -

NOT

CL

‘_

standard

-

refers .

._-

;-

_.

The..estimated

parentheses ._ .. .

:

..

: ,__

‘

:

to

_

deviation

the-last

decimal

__ -.

_.- i,.

._ .:.

.

.

:_

-.

-_: _-.

:_-

_>'__., : with

y; I-..' :: the unit

horizontal, 2

axis

points

:

:

7

_.

_’

-:

f

;.

-,

..C’.

:

i :

of the molecular packing -: ._ '. . ; ? :.; _i. . --.;.:ti:..: _. .P. _.I_: cell 0utlih'ecC The & axis is

the

c

axis

toward

is vertical,

the

reader.

and

the

the di_snbstituted,phenyl

i&e .

of

geometry

normal.

riog

of

to

ring

"egg-beater"

complexes

of

is not

eclipse

direction. the

plane,

PtP;

the

groupa

out

plane

The

one

in

another

atoms

PR(5),

-1.44

and

of

that

predicted

planarity

large

of

order

in

about

the

mizes-the

and

Figure

this

along

reflected

a

indicative ring. ligands

P-C

bonds

the

P(-1)-P(2)

in

phosphorus

PH<4), %,

approxi-

the

distances

atoms)

from

the

displacements

and

PH<3)

respectively;

1 and

lack

planarity

by

are C(8)

ligand

map

the

for

be

for

t1.53, is +0.19

a

the

group

[l].

i

the

this

moiety as

is a

conformation betveen

the

exact

distinct

of

ligand the

energy, clearly

torsion

of

carbomethoxy

remarkably

trans-1,2-dicarbonethoxyethenyl

six The re-

effectively

one A

un-

The

entire

electronic

was

Simple

delocalization

the

z-system.

is

unusual.

that

described

This

Hine

also

require

interaction of

and

is

of

vinyl

stereochemistry

Clark

minimize

bond.

portion

o-bonded

cis

distortion

electrcnic other

the

vould

thereby

C(l)-CC22

and-the of

the

vieved

the

to maximize

out-of-plane

vealed

is

in

substituted

out-of-plane

observed

arguments

v-electrons

and

1161

metallocpclic

Rather,

to

of

opposite

in

116O

B.

the

planar

of

ligand

also

-0.13

that

be

angle

triphenylphosphine

PH<2),

in

valence-bond

the

of.the

Pertinent

R.

ligand _orthometalated

the

vhen


stereochemistry

of

an

phosphine

within

I.

is

expected

lack

~to form

cis-bistriphenylphosphine

geometry

PH(l),

-1.42,

of

other

plane

+1.42.

within

C-P-Pt

straio

observed

This

carbon

triphenyl

angle

arrangement

characteristic

of

monohapto

triphenylphosphine

extensive

mately

the

au-expected

monehapto

the

The

of

The Pt-P(2)-C(8)

compares

normal,

intersect

D,

1,09O.

The is

ring,'plme

75.72O

minigroup

similar ligand

135 Ii73

has

hydrogen group. in

been

observed

bond

involving

Presumably,

I produces

assignment

to

the

of

its

of

an

oxygen

atom

planarity

features

intramolecular

of

which

of

the

lead

of

the

geometry

the

four-atom

the

geometries

of

the

metallocyclobutene

rings

151,

Table

radii

the

N-X

and

C-X

angle

5.

centering

on

metalated)

iridium

Detailed

have

5.

appeared

butane

of

The

the

platinacyelobutane

ing

two

angles

related The 0.082

angle

angles

within

average i

CCH3)312C12 weakly

longer

E217

pt-p than where

trans-labelizing

in

IrBP(Ph)2C6HgCR3-

P'Fr6(Ph)=CcFz=

to

in

longer atom

that

the

is

covalent and

X is

of

into

cyclopropane rings

are

the

Table

puckered, 5 are

in

the

phosphorus bis(ortho-

is

0.17

length

X-C-C are

four-atom

I is

approximately

bond

length,

2.330(2)

the

average

Pt-P

ligand-

Based

for

are

smaller

The than

platinacycloI and the

those remain-

18" than

diflarger the

complexes. %,

bond

ligand on

the

drastically

approximately 14*

phosphine

the

however

platinacyclobutane

each

within

il.Shorter

angles

rings

rings

flat.

of

similar

of

metallocyclo-

virtually

I

and

within

the

[I97

differences

when

I

representative.geometries

rings

the

is

smaller

single-bond

angle

Pt-C-C

the

then four-atom

X-Pt-C

for

the

in

163,

similar

length

carbon-carbon

within

ring

consistently

platinum

in

bond

Pt-X-C

is

the

Whereas

described

The

erroneous

(II).

complexes

complexes.

ferent.

X,

of

insertion

aromatic

average

atom

of

are

strikingly

EZO].

rings

C(7)-C(8)

distances

complex

platiuacyclobutaae butene

a result

tabulations

from

the

Pe3(CO>8(ph)2PC4
As

I is

of

Ligand

rr(C~a~~2P(P~>*(C6H4~P(P~~~-l~5

and

f181,

in

products

of

rr(Co)2P(Pb)2C6s4P
geometry

ester

vinyl

to

comparison

f63,

one

stereochemistry.

presented

is

lack

spectroscopic

~Cp(Phf3f2(IV)

and

ketonic

of

A

(Iffa)

the

a consequence

this

(CgW4)2p(Ph)3(II)

The

as

the

observed

length is

In

in PtfP-

opposite

Cruickshank

a

I

: ,’

tu :

aJ : ,

. i

4c , ,

v f *

d-2 I.

137 criteria

[22]

nificant. to

the

this

The Pt-C

Pt-C(1)

of

a

ligands,

as

ii.

The

this

is

is

highly

i,

in

identical

trans-bromo

by

O(3)

The

authors

Robert

and

K.

Waals

bond

is

Welch

lengths

in a-zXT§-'

triphenylphosphine

and

Manzer

[24].

H(27)-.-H(ll),

contact

distance

involving

3.41(l)

;i.

no

shorter

radii

within

zz.binr

distance,

are

gratefully A.

Pt-C

strain

the

significantly

der

The

Clark

.-.C(41)

van

the

:ryb&+%-&

non-bonded

distances

respective

and

than

contact

The

[23].

V2

Appleton,

sig-

virtually.

from

Pt-P

w,

shortest

contact

work

the

bonded

atoms,

Ac.Xc.~~_u~~n.~. of

I

results

Thus

by

non

nonhydrogen

the

11.7,

2.022(S)

trans-influence

predicted

2.26(l)

bond

>&?J

stronger

shortest

molecular of

Pt-C(7)

&Xr

exerting

two

in

length,

ring.

waous5*&

is

bond

the

metallocyclic

The

length

=

bis(triphenylphosphine)platinum(II)

lengthening

I

AIL/uzZ

bond

(styrpl)

(trans-styryl)

the

difference,

Thus than

inter-

the

sum

observed.

acknowledge

Foundation

the

through

support

Grant

AE-544.

References

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(1976)

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