Structures of organo-transition metal complexes annual survey covering the year 1973 (part 1)

335 ~smzucms

OF ORGAN~-TRANSITI~N.METAL

ANNUAL SURV?ZYCOVERING

!L'HJZ YEAR

comximzs

1973

(PART

I)

M.I. BRUCE*

Department of Inorganic Chemistry, The Dniversity,'Brikol

BS8 1TS

Abbreviations acac

acetylacetonate

biw

2,2'-bipyridyf

bzac

benzoylacetonate

cod

cycloocta-1,5-diene

CY

cyclohexyl

dba

dibenzylideneacetone

dbm

dibenzoylmethanate

DCP

dicyclopentadiene

diglyme

(MeOCH,CH2)20

dppe

Ph2PCH2CH2PPhi

dppp ER

f4asp

2

= PPh2 in

fbfars

RR2 = AsMe

ind

indenyl

nbd

norbornadiene

PY

pyridine

P=

pyrazolyl

sP

-o-CH2=CHC6H4PPh2

terpy

2.2',2"-terpyridyl

*

2

3

=2 P2

A&e2 ER

2

Present addres.s: Department of Physical and Inorganic Chemistry, University

&f Adelaide, Adelaide, S.A. 5001,. Australia..

Referencesp.385

333

.'

-to1

to1y1

TPP

..

.tetraphenylporphin

triphos

MeC(Cli2PPh2)3

-vinyl alcohol

VA

Introduction This complexes

review

determined

follows

the pattern

parts.

The

the general

by X-ray,

increase

number

of

Simple

metal

year's

survey,

and

rapid

growth

in this

area

associated

structures

reported

carbonyl

below,

1

forms

a distorted

anion

is .a distorted towards

geometry

(l),

of

trigonal

the

in the i-01(4);

c-o,

reaction

cleavage

the The

by

the

170.

two phosphine

bridge.

Fe-H

ligands

in

complex;

the cation,

equatorial

and

(3) and

of

are

the

salt,

CO groups

is 1.57(12)g.

is probably

Re(CO)5F.ReF5

geometry

(Ph3P)2h'+

distance

Re2(CO)10

Discrete

The

in its

three

HCo(C0)4 between

2

two octahedrally-coordinated

and being The

similar. ReFs

in anhydrous

l-E

[Re(C0)6]+[Re2Pll]-.3

rhenium

[Re(CO)S] + and mean

dist&ces

with

Vaska's

atoms

are

[Re2Fll] - ions are:

linked are

presen

_.

.-

Re-C,

1_13<3)Z. Sulphur

..

determined

hydrogen.

complexes,

the

fluorine

second

been

isoelectronic

two

former,

by a bent

the

bipyramid.

bipyramid.

the axial

afforded

In the

four-circle

is shown

approaches

by

C-Mn-C, 153O], so that the MnC3P2

trigonal

(2) has

The has

caused

In the planar Mn(C0)3 portion, the trans CO groups are 'bent

[!Se(CO)J-

bent

in two

(undoubtedly automated

methods

derivatives

towards the hydrogen atom bngle fragment

diffraction

facilities)

which

metal

is presented

of suitable

computing

In DMn(C0)3(PMePh2)2

trans.

or electron

neutron,

in availability

and

of organo-transition

last

of

continued

diffractometers

of structures

dicyanide

of &q S-C.bond,

to give

reacts

Ir&l
complex_with

(PPhg)2., containing

337 ph>p/Ph bble I /H

Oc\ OC

/Mn,

\I Fe-co

\F//\ I F

H

Ptl/P\Ptl 1 Me

thiocyanate;

(3)

on recrystallisation, 4

N-bonded isomer (4) occurs.

co.

Oc

(2)

(1)

S-bonded

\Re&cO~..

F'

I

OC

i0

Oc

‘\ne/F I

/

Co

I

FY

z OC

isomerisation

to the

The CO group is disordered with tram

Cl, and CN with the NC of the thiocyanate group. Complexes

containing In

(Cd)

and

probably

' due

The

two Cd-Mn

The

although radii. vary

by

the bond Comparisons

considerably

the empty

bond

(S), both

the does

trigonal

is shorter of

the

than

In paorbital

and

differ

the

radii

with

filled

6

of

considerably

The

of metals

indtcate Some

equatorial

ic

of p

c oC;c,-co OC

Occo

oc

‘;,~~yJo-co

OC-_Mn-CO 6’

these

interaction

\ /c”

that

0

‘Co

&f/

covalent

carbonyl-C

/

ON-

bond

interaction,

single--bond

Oc /” &Mn-CO

+z

In[Co(CO)4~3

In-Co

0

%?

2.799(5)g]

for

bonding the

bipyranidal

is 132.4(2)O.

structure

substituent.

in-plane

are

[Z-760(4),

dn-pa

sum

elements

trigonal

Mn-Cd-Mn

planar

any

covalent

(0.07-0.23~)

the

determination.

suggest

Group

the metals

the angle

structure not

of

lengths

forces;

suggested

c2.594<3)$


(tin) environments

to packing

(6) is confirmed

bonds

(terpy)Cd[Mn(C0)5]2

octahedral

distorted.

length

metal-metal

/

‘co

&

CF 0

(4)

(5)

(6)

Referencesp.385

-~

.- 338’

:.:.

orbitals-

is suggested.

An

in Tl[Ko(C0)3(C5H5)]3,

(7),

_

significantly-[rrange; interactions

were

two

SiH2

(SiH2)]

groups,

although

bond

length

individual.values

2.938(2)-3.001(3)ZJ.

No

reaction

betveen

(8) , in which

2

vith

The

any

Ti-Si

at

least

between

lengthening.

of

the

effects

balanced, SiMe3

and the

by

the

bonds

(9)

-:-.

._

Si-Mn

resulting

two

and

titanium

lengths

of

KSiH3

atoms

affords

are

bridged

by

2.159(13)g.8

(Me,Sil,SiMn(CO), bond

bonds

length

from

the necessity

ii-Si

Me

.;... . . .I_. .:.

of

CO groups'.

Me

.’

metal-metal

(8)

structure

features;

electronic

is found7

differ

other

(C+,)2TiC12

(7)

unexpected

of 2.965:

found.

The

[ (C5H5) 2Ti

average.T1-MO

Such

(d-d)a --

(9) shows

[2.564(6)2] bonding

to minimise

steric

interactions

also

[2,374(S)

suggests

are

-vs. 2.352(3)x

no that

outweighed,

repulsions lead

to

in Si(SiMe3)4].

or

:

339

The- complexes

Mn2(CO)S(SiPh2)2

110) contains a planar Mn,Si, rhombus

in which the-formation of a strong Mn-Mn bond is evidenced both by the acute Mn-Si-Mn angles

[73:4(1)"] and the short Mn-Mn distance of

2.S71(2);;?' The structure of BrSn[Co(CO)4]3 (11) confirms the absence of any Co-Co bonds;

the relative bulk of the COG

a reduction in symmetry to C groups. l1

3'

mini&sing

groups results in

interactions between

CO

The complex [(?le2Sn)Co(C5H5)(C0)]2 (12) contains e Co2Sn2

rings, with angles at cobalt and tin of 78 and 102O, respectively.

12

By comparison with the related complex [Me2SnFe(CO)3]2, in which the Fe-Sn bond length is 2.64:, there must be considerable n-character (multiple bonding) in the cobalt-tin complex, in which the Co-Sn bond length is 2.54(2)g.

(12)

The optically active complex (+>-PtCl[SiMe(l-C10H7)Ph] (PMe2Ph)2 has structure (13) with absolute configuration (S), corresponding to that of the CR)(+)-Me(l-CloR7)PhSiR

from which it was obtained. 13

Cxidative addition of Pb2Ph6 to Pt(PPh3)4 affords Pt(PbPh3)2(PPh3)2, which in dichloromethane

slowly decomposes to cis-PtPh(PbPh3)(PPh3)2

(14):

This complex can also be obtained directly from LiPh and Pt(PbPh3)2(PPh3)2The

cis

configuration is found by an X-ray study, which reveals

Pt-?h and Pt-Pb bond lengths of 2_055(3) and 2.698(9)x. respectively. 14 Referencesn. 385

.>-340 -: ‘, .,

A&3_and -(each-pith : structure arsenic -the

_. ..-:

..

T&tic& Fe(C&5

cluster~ckmpl~x_As~[~&
at-i2O0

,- Fists

one-half-occtipancy), conkists atoms

acting

_. : in the

distributed -.

of a triangular as

crystal

Fe

triply-b.ridging

3

(CO)

(15), in

two.orientations

randomly.

9

cluster,

ligands,

obtained-from

lying

.Basically,,-the with

the

above

two

and

below

Be3.plane.

Ph

Ph

\

/ Pb’

Ph’--P-;t / Ph

\

ph/pyhph (14)

(13)

one

CO

hidden

by Fe3

=-

/co

y 0; (16)

CO

.-

Ph Ph

: 341 .Metal in THF,

followed

afforded

is O-bonded

Croup

attached

highly

asymmetric

structure

The

are

new

staggered

equatorial

W-W

and

not

angle

of

atoms

in HReCr(CO)10 not

colinear

with

wLL

the

pyridine,

complex,

the

first

of

(19).

example

the metal

The

atoms.

reaction

(C,H5)Ni(CO)(PPh,)Fe(CO)3

two

..

to'a

V'-CO,

(a) the

HW2(CO)g(NO)

W-CO

also

bridges

distance

the hydrogen

bonds

two

of the V-V

17

hydride

axial

and

2.42(1)x].

order

CO group.

probably

(C5H5)V(CO)

a bond

bridging

atom

Re-Cr

(18)

bridges gives the

the

long

a W-H-W

two metni

is 3.435(1)x,

is considered

and

to be

19

between

diphenylacetylene

results into

1.94(l);

the hydride

the

reveals

a metal-metal

[V-CO,

of-the

hydrogen

located,

(17)

at present;

groups;

A single

insertion

clear

via

nitrosyl-carbonyl

directly

The

and

this

(C5Hs)2V2(C0)5

nature

intersection

o 18 159 .

although

groups,

CO groups

(b) the precise

bond;

In 16

from

aluminium.

of

bridging

two points

and

than

Hg[(C5HjH,)Mo(CO)3],

the product

(16):

group to a (C H )V(CO) 2 55

moiety

group,

2Mg (pyj4

and

Metals

The

bond,

of

to the MO-CO

metal-other

(b) To Transition

However,

be.wtween magnesium

by recrystaliisation

[(&5-C5H5)Mo(CO)3]

magnesium Main

exchange

in replacement

the Ni-P

bond

and of

to give

the bridging

the unusual

CO

complex

(20L20

%F \y

ocOC’x/

-co

I

/&\

9j_>Iir C

co-. TCO

oc-

1.

Re,

’ co

c

-co

0

cc0

c

6 (18) x=codrNO H lies between

Cl01 W atoms

Referencesp.385

.:

‘_a‘+ .-

:.

..

. .

.,

;

,_

-

1

:

-..,-The.full-detaifsof the structure.of dichloromethane-

. solvated

[Rh(CO)(PPh-) ] ,322

21. have been-given;

,The:complex is characterised

by the presence of-a-Rh-Rh bond- [2.630(1)x], bridging CO groups which may

intera&with-the-solvent

.via &C-O---H-CHC12

hydrogen bond, and an The homo-

unusual five-coordination geometry for the metal atoms.

geneous hydrogrndtiou catalyst [(C5Me5)RhC1]2RCl (21) contains bridging

atoms,

hy-drogen and diloiine

both of which were refined. 22

The RbHClRb

unit is.pIanar,- with the Rh-H-Rh linkage best described.as a three-centre, two-electron bond.

The Rh-Rh distance of 2.9064(10)2 suggests some

metal-metal interaction, which is supported by the Rh-Cl-Rh angle of 73.20(6)O.

The

Rh-H bond length-is 1.849(47)i.

Me

Ph /

Me (21)

(20)

(c) Cluster complexes A.complex Ru~(CO)~(BU~C~H). e.ud Ru3@O)12,

obtained from the acetylene

has structure <22), in which the acetylene interacts

with two metal atoms with a p-type bond, and with the third by a u-type bond.23

.Full details of the structure determination of (azulene)Ru3(C0)7

(23) have been given.

24

The.bicyclic hydrocarbon is attached to one

metal. atom via an essentially symmetric n-cyclopentadienyl

group, and

via a delocalised bond between the remaining five carbons in the C ring and the other two metal atoms.

7

An analogous situation has been

described in bis(pentadienyl)dinickel.

25

3431’.

Preliminary crystallographic data, includ.ing the dimensionsof

the central cluster, haire been given for H~OS(CCH~)(CO)~

(24), derived from a reaction.between Os3(';0)12 and ethylene.26 Me Me,,&Me.

(23)

Interesting_ly, the complex is asymmetric; are different
and

the

two

the two metal-hydrogen

vinylidene

protons

atoms

exchange.

Of the many unusual condensation products obtained by pyrolysis of Os3(CO)l2. 27 the structure of 0s6(CO)18 reported.

28

(25) has now been

The central metal cluster is based on an 0~4 tetrahedron,

two faces of which are capped bythe other metal atoms.

The various

OS-OS bond lengths [range 2.732-2.836(1)2] reflect the coordination number

and

formal

oxidation

state

of

the

metal

atoms.

A

brief

comparison of MO with polyhedron skeletal electron pair theories is made, and predictions of structures of OSCAR made, and substantiated in the former case.

R.eferencesp.385

and O~g(C0)2~ are

-344..

1

-..

.., A trig&al

&e~nkz

_. prismatic metal cluster has been.found.29. in

carbido:cwplex'.[~e3(CH2Ph)i2~Rh6C(C~)15]

(2;).

Each edge

06 the prism is bridged-by-a CO group; each-metal atom also having one . terminal CO group:

The carbide carbon is at the centre of the prism.

The Rh-Rh bonds are of.two types, within the basal triangles [2.776(3)x], and between them [2-817(2)2].

The prismatic geometry-results

from the

impossibility of accommodating

the 90 outer valence electrons in..an

octahedral cluster (maximum 86?, and an interpretation of the structure in terms:of the polyhedral-skeletal

electron-pair theory is given.

The direct reaction between phosphorus and (C~H~)CO(CO)~ afforded a low yield of @o~(C~H~)~P~] distorted Co4P4 cube is found. tvo types of Co-Co distances:

(271, in which a tetragonally-

The distortion results from there being two at 2.504(2)g, corresponding

two-electron bonding inter.action, and four at 3.630(av)& bonding.

Comparisons are made with the isoelectronic

cluster, and the suiphur-cobalt analogue which does not have any net metal-metal

which are non-

[Pe4(C5H5)4S4]

~CO~(C~H~)~S~~. interaction

to a

In the latter,

(see below), the

electron- differences are reflected iu chemical equivalent Co-Co distances and cubic Td geometry found in the latter, together with '. .. long S-S-contacts [compared with relatively short P-P contacts found

in -<27)].

:

..

345. Comparison of the geometries of the clusters [CO~(C~H~)~S~~ and its monocation

(28) gave information about the-antibonding'

character of the unpaired electron. contain

any Co-Co

The neutral cluster does not

electron-pair bonds, and the CoqS4 core -has cubic =d

symmetry, with Co-Co distances of 3_295(av)g.

The cation is tetra-

gonally distorted (idealised D2d.) with two long (non-bonding) Co-Co distances of 3.330(5)2, and four shorter ones of 3.172(5)g.

On the

basis of a metal cluster MO model, the observed distorriod and shortening reflects an increase in individual Co-Co bond order from

0

to 0.125, with a total limiting Co-Co valence bond order of 0.5. Olefin complexes A comparison has been made between the structures of nickel-olefin complexes LNi[P(O-g-tol)3]2 C2H4)32.

(29)

(L = CH2:CHCN and

In the former, the acrylonitrile is more.strongly bonded

Neutral

(28)

Ni (o-tot&P’

‘P(o-tol)3

:0

Cation

a

2.230(21

2.221m

b

2.230(2)

2.215(5)

c

2:232(2)

2.217(7)

d

3.315(2)

3.3300

e

3.236(l)

3.172(5)

nickelman

is -ethylene,-and-in additionthe ..

maximise. the inte+ction

CE the

geometry-is altere'd to

CN group-with-.the

Ni-olefin

This.

bond.

: is

thought to be an-electronic effect resulting from the stabilisation

of

the olefin

* TF orbital

by

the

a-sr.
Cl4

group,

is consistent with the

and

idea of metal-olefin bonding.

found in the complex (CH2=CRCh)Fe(C0)4.

bond distances in 24 olefin-metal complexes

A similar

A comparison of C=C

(of Ni", Pt”,

PtII.

RhI, IrI

and Fe") is also given. The complex [Ni(PCy23(C2H4312 (30) contains a nickelo nickel bond [2.388(l)A] bridged by the two phosphido grOUQS; the tvo olefins are coplanar with the central Ni2P2 group.

33

The angle at

phosphorus is 67.6O. The composition of dibenzylideneacetone deQendS

QallsdiUiII(o)

On

Solvent,

(aba) complexes

and when isolated from dichloro-

methane or chloroform, the composition is Pd2(dba)3.solvent. 34 cH2C12.adduct has structure (31).

The

Each palladium is trigonally

coordinated to three double bonds in bridging dba ligands;

one of the

ligands has the symmetric syn,syn conformation, while the other two are in the =,

trans- form. Vinyl

conversion

alcohol(VA)

to acetaldehyde)

by

of

can

be.stabilised

complexing


to metals.

respect The

to

structure

of

347. .[PtCl(acac)(VA)] mediate

(32)

between

evidence

contains

a v-olefinic

of a rapid

.the alcohol and

solution

bonded

a-aldehyde,

in a manner

‘.

inter-

consistent-with

NMR

equilibrium:

Ho

+

M-D2C,D

35 and

explained

Structural

by

data

a bonding for

model

twelve

(52a)

intermediate

olefin-platinum(I1)

between

a-complexes

the

are

2

compared.

Y/“’

“\/”

i-j&

Me@+--C

OH

\

H,,y ,-C

extremes.

~N,c,s

Cl":

I

H2dCH2

(32a)

(32)

The

reaction

a complex Diene

between

(33)

@tC12(C2D4)J2

containing

and

N-bonded

(33)

di-t-butylsulphurdiimine

sulphurdiimine,

trans'to

affords the

ethylene.

complexes Bond

to those units

in the

are

planar

distances

related but

and

angles

in Fe(CO)(C4H6)2

cyclohexa-1,3-diene

not

parallel.

38

complex

The

structure

37

(34) the

;

are. similar two diene

of IrC1(C4H6)2 40

(35)3g Some

is not

Ir-Cl

significantly

distances

IrC1(C2H4)2(~~), The dicyclopentadiene Referencg

p_ 385

different

in.other

IrC1(C2H4)4] absolute

(unpublished) are

the rhodium structures

analogue. ftrans-

also 'given.

configuration

(endo-DCP)

from

hasbeen

of

the

determined

dissymetric via

olefin

the molecular

endo-

-

36

(37)

structure

of (+)-[PtC12(*-DCP)]

(36).41

between crotyl alcohol and K2PtC.14is cis-PtClp[(CH2=CHCHMe)20J

(37).

A product from the reaction

the ether complex

The ether is coordinated as a diolefin;

during its formation, isomerisation of the original crotyl group occurs.

42

Acetylene derivatives The

photochemical

reaction

between

C 2 Ph 2 and

(C5H5)W(C0)3Ph

affords the carbonyl-free WOPh(C5H5)(C2Ph2) (38), containing a n-bonded 43 acetylene.

The formal electron deficiency of this molecule is reflected

in W-Ph. W-C Ph and U-O bonds shorter than normally found. 2. 2 The unprecedented formation of a n-cyclopentadienyl

ligand

from diphenylacetylene

is found in the reaction-of the latter with

Pd(OAc)2 in methanol;

also formed is PhC(OMe)3:

product, formed quantitatively,

44

is Ph2C2bd(C5Ph5)]2

The metal-containing (39). which is

structurally analogous to the long-known nickel complex, Ph2C2pi(C The-complex anion in K[PtC13{Et2C(OH)CfCC(OH)Et2)] .the.exjected square planar structure (40).45 2.18(3)&

i.e. not..significantly loverthan

H )] 55 2'

has

The CZC bond length is

an uncoordinated acetylene,

aLthough.the._angles of:.the acetylenic carbons..CEC-C, average 160°.

Ph-j--.J-,‘--., ‘__- * :

.Ph Ph

Ph (38)

(40)

The location of the hydroxyl groups makes

it unlikely that any

significant stabilisation of complexes of hydroxyacetylenes via hydrogen bonding, although oxygen-potassium

is achieved

interaction may be

important in this respect. Complexes derived from electron-deficient olefins and acetylenes The structure of Ir[C(CN)=CH(CN)](CO)[C2(CN)2](PPh3)2 has been determined. C-C

portions

of

the

46

(41)

Of interest are the bond lengths of the central

C2
and

C(CN)=CH(CN)

moieties,

which

are

equal

Both cyanocarbon fragments lie in the trigonal plane.. As

@.29(2)Q.

expected, the dicyanoacetylene average angle EC-CN

ligand is no longer linear, with the

139.5(13)O.

This interesting paper concludes

with an extensive discussion of the bonding of vinyl and acetylene groups to metals.

Ph \/ CN

H-C’

Ph

.

\I /co C-Ir NC/ &Lc NC’

‘CN

I f=fr--Ph Ph

(42)

(41)

Referencesp.385

r

:

..

350

-. The

excess

C2F4

to give

determination three of

2

each

(CF ) .32

in which metal

that

atoms

C 2F 4 ligand I-

olefin,

CF2 has

being

plane

has

bond

complex;

to those

been

not

react

bent

back

cross-ring

(43).

The

The

previously,

by.42O.

the

site,

but

A nickel

seven-membered v-interaction

structure

may

be

all

47

to the metal. found

with

the-structure

is no vacant-coordination

coordinated

is a significant

a'nd the double

(42) does

ring

shown 48 to contain

F

that

there

is similar

been

there

Ni(C2Fq)(triphos)

a five-membered

reveals

phosphorus

the

of C

complex

bonding .in the

derivative C Ni.ring, 6

between compared

the with

I

of Rh
a C6(CF3)6 the metal molecule

product

molecule

bonded

is sited exhibits

from

hexafluorobut-2-yne

to platinum

underneath fluxional

'CPCF Re 3

via

the ring

only

plane.

one

Pt(PEt3)3

double

In solution,

contains

bond

(44);

the

48

behaviour.

Et

3

(43)

Comolexes

and

(44)

containing

allylic

groups,

and

other

extended

acyclic

x-systems An from

MOM

clathrate via

the

X-ray

and

be represented

group, as in

Ph3PC2Nn(CO)4BrSl].

50

of Mo(CO)4(Ph3P:C3H4)(C6H6)

Ph3P:CHCH:CH2]

of benzene allylic

study

and

complex

revealed (45).

.resulting.in (45a)

[cfl

that The

the

crystals

phosphorane

a xwitter-ionic

th e organophosphonium

[obtained are

a

is coordinated

complex

which

acetylide

may

complex,

\

OM;(46)

C45al

(46) (monoclinic form)

The complex Ru(C~B~)~@
52 has a similar structure to that of Ru(C~U~)~(PP~~I~ reported last year.

!j3

The bonding of the Z-methallyl groups is asymmetric, with Ru-C

distances of.2.38(2) (trans to P) and 2.28(2)x (trans to C).

The

methyl group-is bent out of the ally1 plane by 12O away from the rnetal atom, in contrast to other metbaflyl complexes studied. Crystal data for an orthorhombic form are given. and [iC3H$iC1]2 afford (Dihydropentalenylene)dilithium the binuclear complex (47), in which the two Ni(C.&) 54 transoid configuration.

They are closest

units have a

to the non-bridged carbons

of the bicyclic Ligand, which is nearly planar.

Complexes containing cyclic C3 eC4

systems

+ Addition of C3Ph3 FFg- to PtfC,R,)IPPh3!2 affords the new cyclopropenyl.complex fPt(c3Ph31 (PPbj).JPPg <48>, containing a' Rereffrtcetip.385 ._.

.

,_

”

.

.

_,

.3”

:_ :

I

I

-localis+ :

:

:

y_

CYc~oProPenYl

55 king-asynimet&callybonded to the metaf,

:PtLC distances- are 2.09&

m. .. : :

while the-third is 2:48(1)x, suggesting.

.-

that the complex is,best described as involving bonding.from a

_:

:-

localised double-bond in the.Cg ring,

:

_-

: In (x~CgHg)Rh(n-CkPhq)

(49), the phengl gkwIt&e~twisted

'.-

(49)

(48)

relative to the C4 ring, and bent away from the metal atom.

56

The

plans of the C4 and C5 rings are.intersect at an angle of 2.4O. Iron carbonyl derivatives of unsaturated hydrocarbons The structure of the unsolvated 1.4-diphenylbutadiene complex (50) has been determined.

57

(L)

The first-formed of the two

complexes obtained from 1,4_diphenylbutadiene

and Fe2(C0)9 has been

shown to be the "solvated" complex L.Fe(CO)3.jL_58

Comparisons between

_

the two structures show few diffe.rences. The Fe(C0)3 derivative of I-Carbethoxy-lH-diazepine

has structure (Sl), in which the iron is

bonded to the C4 diene unit of the ring.

Phv

59

/ ----\,.-=2

ph

I

iI

OC

..

EQl_

cO

.-

(57)

(52)

353 .. The confirms

L6,7,8-h4

the proposed The

bicyclop.Z.O]d atom

The

and

recourse

62

hydrocarbon by X-ray

It is reported all

complex data that

as good

carbons,

isolated

(54-57).

Some

crystallographic

working

or better

of

in the

encountered to reveal

time, than

total

they

and

would

C

from these

the

he

atom,

61

of four

reactions were

be.tween

completely

without molecules,

conventional actual

elapsed

metal

(C3Hlo)Fe2(CO)6.

of fluxional here,

iron

ring.

4

structures

methods,

case

second

in the

outline

of eight,

be unlikely

to the

involved

the

= *-

(53)., in which.one

and

60

derivative.

(CloH12

(C3H3)Ruz(CO)6

reports

structures

"the

not

of

methods;

would

structure

carbons

to those

to spectroscopic

the more

are

other

of a total

directly

spectroscopic

cost

this

has

.]

(52)

(heptafulvene)Fe(CO);-

C10HlzFe2(C0)6

adjacent

communication

complexes,out

identified

or of

to the is similar

Aninteresting

Fe2(C0)9

molecule

to three

is bonded

of

as a trimethylenemethane

e&2,4,6-triene)

structure

more

structure

fluxional

is attached

which

isomer

time,

structures. and

direct

in a classical

approach".

(55)

(56) Referencesn.385

~

~. 354

. Irradiation 0f,-(l,2-C2H2Br2)Fe(CO)~ in solution afforded._

63 the binuclear complex C21i2Dr2Fe2(CO),. shown to'have. structure (58). The two Fe(CO), moieties are linked by a.metal-metal bond (2.5252) bridged by bromine; and a n-bromovinyl group, although the bonding of the latter suggests formation of a 1-ferra-n-ally1 system.

(58)

The interaction of Me3SiI blth Na2Fe(C0)4 has given a complex initially formulated as [(Me3Si)2Fe(CO)4]2. but shown to be the ferrole complex C4(OSiMe3)4Fe2(C0)6

(59) by an X-ray study-

64

The

structural features are similar to those found earlier in C4(OH)2Me2Fe2(C0)6One of the products obtained from this ferrole complex and diphenyldiazomethane has structure (60), chloramine T and the ferrole.

66

analogous to the product from

The diagrams (Figures 1 and 3) in this

paper actually relate to the isomeric product also isolated from the reaction, and described in a previous paper (J.C.S.Dalton, 1972, 2169). Dr; Jeffreys has kindly supplied the correct diagram, which is given here.

65

Cyclopentadienyl

complexes

In Sc(C5H5); 5 & -C5H5 resulting

units.67

5

indication

of some

comparison

the

(62),69

portions

ligands,

the

approaching is not

120°.

for

chosen

essentially

of

the

of covalency

in

structure the metal with

bonded

&l-C both

former

bridging

is made.

between

to two

groups,

the appropriate

is symmetrically

and

as an SC-C

68

bonded

In

bonds. tri-

to the C

5

the normals

Cl position

this

H 55

is taken

of Sm(C5H5)S

the angles

in

is coordinated

containing

electron-rich

structure

to secure

of

(unsolvated)

of

coordination

of uranium. carbon

of UC1(C5H4CH2Ph)

a well-ordered

perturbation

individual

via

atom

the

indenyl

complex,

group

as has

been

Sm(iod)3(0CqH8).70 The

was

The

preferentially

suggested

presence

degree

with

metal

arrangement

The

indenylsamarium of

each

to two -others

in a polymeric

terminalc

Some

and

groups,

(61),

the C5 group) 71

positions

crystal,

reveals

The

C5

in the

5 (63) with

approximate

ligands

are

previously

(tb e substituent minimum

electronic

tetrahedral symmetrically

studied

bonded;

UC1(C5R5)5

were

-Ph

(61)

(64) Referencesp.385

&.

.,

.. :

not

72

-.

refined.

1

Tetracyclopentadienyluranikm

cdordinate$:uranium

:

._

atom-bonded

to four

(64) has

ai-tetrahedrally

h5-cyclopentadieuyl

&roups.

-

Paramagnetic.tris(cyclopentadienyl)titanium.(6S)'has

two

:.. pentahapto-cyclopentadienyl-

many bent two

groups

(&s~CsU5)2TiXz

adjacent_

carbons,

as a three-electron

systems; a.lthough

donor,

An M.O.

configuration.. TiC12(2t3-Ph2CsZ3)2

bonded-to.

with

picture

(66)

shows

the -third C

it is suggested the

titanium

no unusual

moieties

diffrac.tion

[CsH4(CH2)3CsH4]TiC12

displacement similar

effect

of

the ring found

with

arenot

hydrogens the methyl

groups

ring

that

74

75 (67)

as found.in.. is .attached

this

ligand

structye

although The

acts

of

the

neutron

reveals

the metal

by

a 17-electron

The

features,

planar.

towards

S

adopting

is presented.

phenylcyclopentadienyl study 76 of

the me&al,

atom

in U(C8H4Me4)&

a slight [cf.

the

Other

i'heph

i

(65)

(66)

(68)

-:_ ..

.- 73

(67)

:

:

357 features, are

in

with

the

with.the-

agreement

dienylhafnium .and is

exception

contains

thus

similar The

been

complex

attached complex

the

Comparisons

Nb-H

with

particularly

metal

a &

5

atom

[1.70(3)x]

respect

to be

distances,

(68);

79

complex

the bridging

dimer.

-cyclopentadienyl Other

Nb-Nb

complexes

cyclo81 and

This group

features

is actually also

of

[3.105(6):]

containing

angle

78

as

(C51i5)(CO)Mo(C5Hq)Mn(C0)4

(70).

to the

formulated

of

niobocene

and

ligands

the hydride

member

in

C-C

complex.

catalyst

another

so-called

21 selected

with

two,k'-C51i5

titanium

80

found

containing

to the other include

shown

also

[(C5H5) (C5H4)=h]2," a hydride

analogous

(69),

complexes

and

larger.ring

study. 77. Tetracyclopenta-

X-ray

polymerisation

[(CgH5)(C5H4)TiHAlEt2]2 pentadienyl

earlier

to the

has

expectedly

two k5-C5H5

olefin

[(C5H5)2TiA1Et212

ofthe

the niobium

bonds.

(C5H5)2M

C5H5-M-C5H5.

are

groups,

made.

(69)

In angle

is 37O,

distance (72) the

was

the hydride

and

assumed

is dimeric

via

trifluoroacetate,

References p_ 385

the

rings to be

bridging with

(C5H5)2Nb(CO)H are

(71),

essentially

1.52.

The

complex

carboxylate a V---V

C5-ring

"eclipsed".

83

dihedral The

Nb-H

[(~-c~H~)V(C~H~OCO~)~]~

groups,

separation

the

as previously o 84 of 3.6258.

found

in

Complexes

containing In

n-bonded linked

the

to each by

complex

ring;

the arene

C ,>7 6

cyclic

and --

C8 systems

C6H6CuS03CF3

the

CuS03CF3

molecules.

(73);

forms

two

infinite

copper

atoms

are

cross-

chains,

85

In (CZ5H5)Ti(C7H,), the carbons of the planar C5 and C7

._ rings are respectively 2.32 and 2.19g is unusually short. [(&.,H~)Mo(CC?~~BF~

86

The

'(74) have

piano-stool-confi@ration, _... .: .__., ‘:

full

details

appeareds7;

vith

a planar

the latter

from the metal atom: of~the

structure

the molecule C7 ring

of has

attached

a conventional to an Mo.(C0j3 .-.

.: .--

__ :. .__

~.

.:.: -

:

.’

359 moiety.

A comparison of MO-CO distances in some 15 complexes shows -.

that only that in Mo(C0)6 is longer than those found in (7$). Further details of -h8-cyclooctatetraene appeared.

T‘ne ion-pair salt K(diglyme)[Ce(C8Hg)2~

derivatives have

has structure (75).

in which the cation is coordinated on one side by the ether, and on the other by one of the CgH8'- rings.

88

The latter are planar. and attached

to the cerium atom so that the molecular symmetry of the anion is D 8d

(75)

(74)

(staggered rings).

Full crystallographic and structural data for

U(C8H4Me412 are now available,

89

In both independent molecules, the

uranium is bonded to planar C H Me 84 4

2-

rings.

The two molecules differ

in the relation of the methyl group, one being staggered, the other eclipsed;

the methyl groups are bent towards the metal-atom, for

which phenomenon two hypotheses are proposed. Complexes containing n-complexed heterocycles The mixture of 1,2- and l,&dihydropyridines by NaBH4 reduction of N-methyl-3-ethylpyridinium

obtained

iodide reacts vith

Cr(C0)3(MeCN)3 -to give the isomeric complexes (76) and (77) as stable NefeIencmp.386

..

“0:.

:

;

examples those

9ti

of dihydrop$ridi&s_

expected

inter&ts:witb

for

alkene

two double

and

Bond

aromatic

lengths

are

systems,.

intermediate-between the chromium

and

bonds aiid.the-nitrogen lone pair with a :

distorted octahedral coordination.

The Mn(CO)5 derivative of P'n4C4As readily loses CO on heating or irradiation to give the tricarbonyl.-"

This has structure

(78); and contains a new example of a x-bonded heteroaromatic system: incorp.oration of the relatively large arsenic atom into the planar -heterocycle causes large angular distortions e.g. CA.&, 84.9(4j”,

and

CCC average 11&O.

Ph

I

6

he

Me (761

\

(77)

(78)

The structureof a cyclohepta[cjthiophene coritaining

a

described.g2

complex [79)

Cr(C0)

moiety attached to the thiophene ring has been -3 In contrast with the free ligand, the tropilidene ring

has the boat conformation.

Details of the structures of the two

complexes (80 and 81) obtained from a cycloheptsfb]thiophene given.

93

have been

In both cases, the Cr(C0)3 group is attached.to the C7 ring,

the bond distances indicating two different conformations, and 6 suggesting jl -attachments in these comnlexes. -During the reaction isomerisation.of the'ligand (by hydrogen migration) occurs, and the structures,.of these complexes help the interpretation of the mechtinism of the reaction.

I : -:

361

Go,

(79)

Complexes

containing The

compared

with

[z.lom~J found

to that length

structure

those

is not

in the of of

metal-carbon of

of related

o bonds

The

the analogous

(a) Simple

~Cr(CH2SiMe3)2(bipy)211 aryls.

significantly

aryls.

(81)

structure

94

different of

The

Cr-C
from

and

(82) has bond

derivative,

(83) with

Referencesn.385

bonds

a Cr-C

Me (83)

(84)

been

is similar

2.087(4)2."

‘(82)

aryls

length

the Cr-C(sp')

[CrPh2(bipy)2]I

2-methoxyphenyl

alkyls

bond

362 The

stereochemically non-rigid complex IrMe(C8Hi2)(dppe)

(Sk) has a distorted trigonal-bipyramidal

coordination about.thF metal,

with the methyl group occupying an axial position. compared with that of IrMe(C8H12)(PMe2Ph)2,

96

The structure is

reported in.1972.g7

The

observed differences correlate with differences in the rates of stereoisomeric interconversion, and with the proposed Berry pseudo9i3

rotation mechanism for this process. with IrMe(C8Hl$dppp)

(8!$Bg

angles are 101.5(2) (ge2Ph),

Comparison can also be mqde

In these three complexes, the P-Ir-P 93.4(l) (dppp) and 84.9(2j" (dppe),

which correlate directly wLth the rates of the stereoisomeric ‘interconversions

(cf. values f&r free energies of activation, AG , which are

16.3, 13.4 and C9.2 kcal mol

-1

, respectively).

+A

I

oc-f-

F5C'

PPh3 CL

PhzaP I 0.

.C

P

oc-I’~cl

\

I /

PPh,

/ Ph3P I CL

(87)

(86)

(85)

H-

The reaction between sodium chlorodifluoroacetate

and

Vaska's complex affords initially the complex IrC1(OCOCF2C1)(CHP2)(CO)(~Ph3)2 (86), while prolonged r&ction

gives IrC12(CHF2)(CO)(PPh3)2

(87).'O"

In the latter, the chloride trans to the CHF2 group originates from the trihaloacetate, perhaps via the cyclic transition state

363 The fulL (88)

contains

with

amines,

a comparison e.g.

Me

Indeed,

complex. bis-adduct

accountlO

3

N-SO

of

c&this and

2'

reaction

the

structure

adduct

with

other

between

metal

of .trans-PtM&(PPh3)21S02

similar

adducts

complexes;such

IrI(CO)(PPh3)2.and

of S02.

as Vaska's

SO2

affords

the

Ir(CO)(PPh3)21S02(S02).

Ph

/Ph

\ Me\

/

Ph-P“ \

J

i

‘\Ph

‘.CH2

‘\I.

0

\-.-Pn

_. S-0

rn-

/,iH>Ph

p--i

I Ph (89)

(88)

The

complex

the reaction

between

a relatively

long

structural

data

a contribution

Pt(C6H9)(CH2COPh)(dppe)

Pt
Pt-CH2COPh

suggest from

and

[2.175(10)511.102

this

bond

has

obtained

acetophenone,

bond

that

the

(89),

some

This

ionic

from

contains

and

other

character.

with

form

pt+---_CH

----PPh---_O2

The

bond

angle

at

rehybridisation, (b) Complexes

expected, one has

been

formed

by

determined

RefeAlcez.p385

atom

via

The

can

G and

form from be

attack

of a palladium

reported.lo3

is bonded

configurations

nucleophilic

structure

diastereoisomeric been

carbon

does

not

indicate

any

however.

The (90) has

the appropriate

Cg

of complex

the X-ray

assigned

is boat-shaped,

The (91)

absolute ([a]

structure,

to the

olefines

hydroxycyclooctenyl

ligand

x bonds.

on coordinated

two

104

chiral

-42.3; and

complex and

as

configuration c 1.2, the

centres,

CHC13)

absolute as

shown.

of

..

Addition

of.dkthy&m.ine~to.olefin-platinua~complexes

rvitter-$onic

[PtCl~(C2H4)(NHEt~)]

has

probably-results

from

shown,

stabilise

which

coordinated group

may NHEtq

has

structure.

The

(92).

the.formation.of the

NHEt2 and trans-

product:from

an Ii:H---Cl-hydrogen The

complex.

the ali-trans

particular~conformation

two

amines

conformation,

while

bond

dikfer:

as the

the NH2Et2+

is gauche.

(c) Products

obtained The

[a-C2(C02Me) (a)

The

c0~1ex.~~~.

affords- a

2H]

the C5 ring

hydrogen product

bond

refined-lo7 (probably

reaction gives

to an ester

confirms

as a result

between

"insertion"

add&

carbonyl

the

the

moiety,

group.

106

into acetate)

asymmetry

of substituent

and

containing

(93),

to a C(CF3)20Fl

as

reactions

hexafluoroacetone

of norbomadiene

(derivatised This

so-called

a 1:l

attached

of insertion

[(C4H7)PdCl]2

by

of

effects

as novel

and The

(a-C5H5)Ru(PPh3)zfeatures

(b) intramolecular

structure

of

the Pd-C

bond

in

(94) has

been

further

the n-vinyl on

coordination

the IT* orbital),

CL

/

0.

Me

the

and

a

365 Me Me

F..

Me

I

,ppve IF

Me

\ Me

Me /

lP-Me \

F' 'F

tie

(95)

(94)

demonstration of the higher trans influence of the o-bonded carbon relative to the n-vinyl group.

Hexafluorobut-P-yne

(L = tertiary phosphine) to give intermediates,

(MeAuL)gC4F6, which

break down to give either cis-UuC(CF3):C(CF3)Me or cis-LAuC(CF3):C(CF3)AuL mediate

(the insertion product),

(with elimination of ethane).

The inter-

(L = PMe3) has structure (95), and contains Au(I) and Au(III),

and a reaction mechanism is proposed. (b) Complexes

containing

108

internally-metallated

ligands

The structures of two ortho-metallated manganese, derived from benaylideneaniline have

reacts with MeAuL

been

described.

In the

former,

romplexes containing

and N,N'dimethylbenaylamine,

P&wn
(961,

a planar

five-membered chelate ring is formed, with equal.Mn-C and Mn-N m distances?" In the second complex, Me2NCH2C6H4Mn(C0)4 (971, the chelate ring is now puckered, resulting from the presence of saturated N and C atoms.

110

Trends in Mn-CO distances in both complexes are

discussed, the shortest being trans to nitrogen. One product from the reaction between E-FC~H~N~BP~ Vaska's complex is the ortho-metallated

aryl diimide derivative

and (98).

111

Dimensions within the five-membered C2N21r ring are similar to those reported for related complexes. Rapid intramolecular hydride addition at the free vinyl group in HMn(CO)4(sp) affords two isomeric complexes, one of which is (Meawn . References

(99). p_ 385

The complex contains a small amount of the

(96)

second

(97)

isomer

to about

(anti-Markounikoff

20 symmetry One

between 2 hrj

phenyl

in this

and

case

phosphines

the

Three

iridium

have

been

I;C6H4PPh2(PPh3)(CO) iridium

metallation structures

carbonyl

of

the three

complex has

complexes

and

i-propyl

occurred,

group

been

undergone

CO-

the

donor

internally

atom

determined

The and

the

one

coordination

is shown

6 carbon

containing 115;

metallated

(C2H4),

complexes

ocrturs at

0 I-

toluene.

the metallated

with

Iwh2(PPh3)

isomeric.complexes have

has

containing

three

the reaction

which

in

I~Pr~(PPr~)(C2H4). in all

rise

113

oxygen.

studied114:

is similar

of

metallation

being

from

(refluxing

,

initial

gives

112

obtained

complex

in the

a second

probably

cis-MeMn(C0j4(FPh3)

tricyclic

group

(98)

which

reflections. products

and

is the unusual

insertion,

about

the many

ph2PC6H4&(CO)6.

phosphine

addition)

forbidden

of

.!

in

atom.

(101); The

metallated (102)

contains

the

no4>

first example

of a dimetallated

tridentate ligand.

On heating

isomerisation to the bis-3lonometallaced complex occurs, formed as ~1s and trans isomers (103, (e) Metallocyclic

104).

derivatives

The structure of Ir(acac)(nbd)3

(105) [derived from

[lrCl(cod)]2 and norbornadiene] reveals that two of the hydrocarbons 116 This complex have combined with the iridium to form a metallocycle.

(106) Referencesp. 335.

:

.;368 .. ..

._

..

:iS considyed

&lie-a*

;

:

intqmediate

in the m&ai-&mited

f

: Spclo-dimerisation

of no&ornadiene

..

.[2+2'1

to the --exo-trans-es0 dimer, which '.

can

be

:

isolated by refluxing Lr.(nbd)8Cl with excess PPh _

-. I.3 T&z_ conformers of a platina-cyclopentenedione- (106)have

been obtained from Pt
117

The two isomers the former is

(deep red and deep blue. in colour) are interconvertible; the more stable.

The major structural difference lies in the twist

angles of the two CO groups about the connecting C-C bond. Metallocarboranes

and related polyhedral borane derivatives

The structure of NMe4[Ni(B9C2Hll)2]

(107) reveals a

symmetrical sandwich-type anion, and completes the series of Ni and Ni is

the

IV

structures.

latter

which

118

Bond distances

accommodate

electronic

in determining

4

Ni n 1.. ’ ’ : ‘, -.* N’,’ I . .,

,’ t

B

; ‘,

differences

between

the stereochemistry of this type of complex.

,-.

[(B C H

9 2 11

)Co(B C H py)] has been 8 2 10

._

Carbor! ..(107).

III

(Ni-B and Ni-C) suggest that it

account of the structure determination of the asymmetric NEt

, Ni

the

three

However, intercage non-bonded interactions are also important

complexes.

complex

II

(108)

.:

given.

119

A full

metallocarborane

The metal atom

369 is ion

sandwiched between the .mutually staggered carborane anions; is

linked to

cobalt

via

a&

open

'h" BgC2

CB_, -face.

Crystallographic verification of.the existence of "tripledecker" sandwich compounds has been obtained in the case of (C5H5)Co[3-Me-<1.7)-2,3-C2B3H4]Co(C5H5) but not parallel; by 4.6 and 5.5O.

(10S).120

The rings are all. planar;

relative to the C2B3 plane, the CB rings-are tipped One C5 ring eclipses the C2B3 group, while the other

is staggered.

. A product from reactions between Mn(CO)5Br and B9H14in tetrahydrofuran 12' is M~(CO)~[B~HI~(OC~H~)]

(x09).

In this complex,

the Bg cage acts as a tridentate five-electron donor to the metal, by *a single Mn-B bond [2.196(6)x], and two three-centre two-electron Mn-H-B bonds.

The zwitterion Mn(C0)3[BgH12(0(CH2)bNEt3}]

formed from Mn(C0)3[B9H12(OC4Hg~

(110) is

by a complex rearrangement, involving

cleavage of the THF group, and a shift of the bond to oxygen from B(2) to B(10).122

370 :...-

.. The -structure of trans-@tClZ(l36HlO)Z (LTl), obtained from and determined-at -170°, reveals that the two

.Zeiseis salt and S6I&, .&on

l@ands. are coordinated via the centres-of,the,B(4)-B.(5) vectors,

which are lengthened from 1.6x (in free B6E&,~to typical of.triangulated polyhedral boranes.

1.82(5)x, a value

123

Complexes- containing donor-atom ligands (a)

Carbon

(isocyanides, carbenes

and related iigands). The complex MnEIr(C@)3(CNMe)2 (112) is nearly octahedral, and bond length data, coupled with MO calculations, indicate that backbonding to the isocyanide ligands occurs even when CO, a much stronger x-acceptor ligand, is present.

124

Several structural studies, summarised

in this paper, indicate that M-CNMe (methyl isocyanide) distances are close to expected M-CN (cyanide) distances.

BI-

Me,

A0

N\

Me’

N

/=

qo+

J--&....qo_

I /=

=\ I”YC

‘0

I C

a

I 0

b

Me

(112)

Me (114) The acetyldihydrofuranyl in &h&h length.

complex (113) has a structure

the C(2)-C(3) and C(3)-C(6) bonds have nearly the same 125

This and other features have been explained in terms of the

resonance structures (113a-c):

in particular, the short 6(2)-O bond,

and.the near planarity of the MnC(S)OC<2)C(3) (oarbongl

.

groups

omitted),

-_

system support form (113~)

C

371 The

FeC~N2B~ring

addition

in

(~-C5H5)Fe(CO)[(CBNMe)2EH~

of borohydride

conformation;

to the

a planar

ring

cationic

(114),.fdrmed

isocyanide-complex,

is precluded

by

by has

a boat

the geometrical

126 requirements

of

the

constituefit

Reaction the

formation

isocyanide lost atom.

The

moiety.

lz7

of-methylhydrazine

of a chelate

molecules,

a proton;

[Pt(CNMe)4]2+.results of

In this

complex

results

can be regarded

of EtSH

with

by addition

(115).

of HCl

ligand

Addition

ligand

as in

addition

complex

atoms.

to the

[l?t(CNMe)J2+

/Pt\ Me /= =, N Me

(115)

(176)

(117) Ftefereacesp_385

to two

nitrogen of

as a chelating

N-N/ H\N_tv\ ,&q N\

one

in protonation

Me

M,/

the hydrazine

cation

this

in

has nitrogen

dicarbene affords

the

312.

1

.: ._..-;1 ~

'methylamino(thioethoxy)carbene.~omplex~(116).

.; .~&a!n~~&rs

Comparison of structural

f0r.a number of related platinum complexes supports -the-idea

that'carbenes .are strongly o-bonding ligands with a trans influence similar to that of. tertiary phosphines.

128

Adducts are formed between silirer salts and metal acetvlacetonates, and the structure of Fe(acac)3.AgC104 (117). with an .. Ag-CH(acac) bond of 2.3g. indicates an interaction of-AZ+ oith the electron pair on the-methylene carbon.

129

A similar feature is found

130 in Ag3(N03)2Ni.(acac)3. (b) Nitrogen The monocarbonyl of the free macrocyclic

(118) has been obtained from the reaction

ligand with iron(f1) in the presence of CO. 131

In this complex the iron atom has a similar environment to that in CO adducts of heme proteins. The system Ru3(CO)12 -tetraphenylporphine reexamined. L32

--\I N’

,

Initially, the lability of the Ru

II

(TPP) has been

complexes formed

,N

Fe-

I\

(118)

PWnyI

/--‘H 'H l-l groups omitted (119)

373 wasinterpreted

on the basis of a ready association of ligands-with

the five-coordinate monocarbonyl Ru(CO)(TPP)(EtOB)(I). r,ee AS72/1:

J.Organometal_Chem.,

More recently- . .

53 (1973) 162-J. complex(I) was

reformulated as the dicarbonyl Ru
A detailed investigation reveals that .the products are

monocarbonyls,

and that the supposed dicarbonyl is in fact the

previously proposed ethanol -adduct Ru(CC)(TPP)(EtOH)

(119), in which

the CO and EtOH groups are disordered. Full details of the structure of Mo[H2B(Me2pz)2](&3-C7H7)(CO)2 (120) are now available.

133

In this complex, the molybdenum attains

the favoured lg-electron configuration by forming a two-electron, threecentre B-H-MO bridge bond.

The six-membered chelate ring is markedly

bent to accommodate this feature.

In the solid state, the complex

[RB(pz)3]Fe(C0)2(COMe) has structure (121), in which the acetyl group is skewed relative to the rest of the molecule. 134

The Fe-N bond trans

to acetyl is significantly longer than that trans to CO, probably as a result of the operation of a o trans effect.

In solution, the

multiplicity of the v(C0) bands indicates the presence of rotamers. (c) Phosphorus or arsenic Three phosphine

The molecule cis-Cr(CO)3(PR3)3 is octahedral, with a mean

examined.

Cr-P distance

of 2.346(3)g.

(121) References p.

.

.

(PH3.)complexes of chromium have been

385

The monophosphine

complex, Cr(C0)9(PH3).

374 .-.

~.

.has-very

sim%lar~'&zll

-&(co),;

135

monimise

to two

indicate..the

Derived

conformations

intramolecular relative

three

n-acceptor

mutually

about

-Comparisons

of structural

near-octahedral

P(OPh)3

parameters

correspond

the Cr-P

of Cr-P

bond

>.PH3

in

the

of

cis

positions

600

strengths:

to: those

shows-a

hydrogen

rotated

contacts.

Comparisons

over

parameters

kf &-Cr(C0)i(PH3)2

136

the metal;

-statistically

&tructu&

is disordered

!l'he.structure

coordinationof

and

.-

PH3 group

the

positions.

dim&ions

axis

to

distances' > PPh3.

complexes

Cr(C015L [L 5 PPh3 or P(OPh)3], which have the expected Cqv symmetry, has

given

ligands. Cr-C

information

137

Thus,

bonds

trans

values

PPh3,

as indicated

with

a W-W

are

bond

the

those by

period

ligand

earlier

central

[3.05(1)A4j,

affords

of

are

group

and

and in

(f4=p)Fe2(CO)

and

and

2.3092,

1.8612,

while

of

the

the

n-acceptor

than

studies.

[W(CO)4PEt2]2

(122)

at phosphorus

c

power

respectively.

is a better

n.m.r.

the angle

the unusual

n-acceptor

2.422

if P(OPh)3 i-r.

W2P2

relative

are-l.845

expected

Irradiation prolonged

the

Cr-P-bonds

to the

These

The

concerning

with

excess

is planar,

decreased

ligand

for

to

a

0

complex

(f4asp)2Fe2(C0)4

(123).

X

375 One

ix&

which iron

atom'is

chelated

a ligand-of is bonded

this

the

fifth

type

to three

one.ligand.[cf.

by-two has

the

the uncoordinated

coordination

diarsine

(trans)

and

character

position

complex

1.885(4)x

(cis

CO group.

Although

the

two

conformers

propane,

Me2As(CH$3AsMe2]

steric

exists

repulsion

as only between

an

The

Cr-CO

of

of

bona.

139

structure of

l-841(4)

s-acceptor

is non-planar.

one

conformer

the

related

(125), groups

on

complex

probably

Me

(i25)

(124)

Me

fac-

as a result

the metal

Me

Referenceap.385

C=C

[L = 1.3-bis(dimethylarsino)-

equivalent,

(126)

second

the

superior

ring

on

of 1.326(8)g];

distwces

the

cyclobutane

Me

The

the metal-metal

bond

reflecting

are

axial

length by

occasion

[l-476(8)2]

determination

of Cr(C0)4L

the

elongated

is occupied

reveals

first

to chelate.

double-bond

to As), 140

the

and

the

ligands,

shown

(-150°)

(124)

of

MnC1(CO)3L

been

CO groups

A low-temperature of

f4asp

(ligand

of in

376

-.

'equator&~'affords ligand

position);

the

.The

binuclear'complex

bridges

Mn(CO)4As

14'

are

bet&en

almost

(126),

in spite

atoms; perfectly

and

Mn2(CO)io

Mn;(CO)8(f4fars)

.the -two metal

groups

reaction

of

this

f4fars

in which

the

feature,

the

two

142.

staggered.

(d).Oxygen The

bidentat

a symmetrical

bonding one

may

from

complex

Mn(MeC02)(C0)2(PPh3)2

carboxylate

ligand,

(127). contains

functioning

as a

primarily

8

143

o-donor.

acetato

Bond

distance

occur

be'tween

each

PPh3

calculations the

suggest

acetate

oxygens

that and

some

hydrogen

two ortho-hydrogens,

group.

Pn Ph

/ ---p/--Ph

OC .Me

(127)

The Re(CO)3C1L complex dbm bond

and

reaction

ligand

has

144

is present.

[Re(CO)3Cl(bzacH)]2

by halogen.'

Using (129)

6-ketoenol

and

the

(128),

bridges

l and

6-diketones The

the

in which two metal

was

obtained,

ligand.

The

is bonded

determination

phenylethylimino-3-penten-4-olatolpalladium

and

one

oxygen

two Re(C0)3 via of

from

type

of-complex,

to -contain groups

the keto

each

No metal-metal

atoms.

shown

affords

dibenzoylmethane

a third

benzoylacetone,

B-ketoenol

The.structure

Re(C0)5C

(L = B-diketonate).

structure

asymmetrically

dentate~neutral

between

Re2(C0)6(L)2

(L = dbm)

(129)

(128)

a mono-

are

group.

bridged

14s

(nmethylallyl)[2-(l&z)+(130)

clearly

distinguishes

377 single

and

ligand

double

bonds, 146

as shown.

and

confirms

the

structure

of

the

ketoimine

-

(e) Sulphur The of other shown

structure

related

compounds,

phSFe(CO)3]2

with

the

The

supposed (SMe)2

Fe2
cluster

two phenyl

and

complex

S2C2(CF3)2

is similar

groups

(in fact,

in the generai

only

space

the

group

obtained

has

been

The

[Pe2(SMe)3(CO)d[Pe21S2C2(CF3)234]. example

(131)

being

to

those

bent

as

147

(anti).

between

of

second Pl.

such)

The

cation

reactions

shown148

structure of one

from

to be

is an

solved

(132)

the

salt

interesting

by direct

consists

of

methods

two Fe(C0)3

Me

Ph

tie (131)

(130)

groups

bridged

Implying metal

atoms

are

the

formation to those

and violet

a square-pyramidal

form,

the CO group

of

the phosphines

and

is also.the

References

P

385

.-

groups,

anion

similar

the orange

SMe

no metal-metal

in the

through

features

have

three

essentially

occurring

Both

by

are

separated

of

two Fe-S

found

isomers

occupies

the

apex,

this

sterically

an Fe-Fe

interaction. by

distance

of

3.062(4)x,

In contrast, 2.767(4)&

bonds.

in other

metal

Other

the

structural

dithiolene

structure.

-whereas

position. hindered.

149

In the

in the violet The

former

two

dimerisation

dimers.

of Ru(CO)(PP~~)~[S~C~(CF~)~]

five-coordinate

is at

most

with

(133) orange

isomer,

is most

one

favoured

-

,378..

:.

.-.

(I 33) Bases

(132)

of square

pyramids

indicated

The complex [(.rr-C5H5)Fe(SEt)S]2(134) contains a planar FeSSFe bridge, and the structure suggests that of the three resonance forms

-s-s-

.s---_s-

Fe3+w

Fe3+tf

Fe2+

I

s=s

Fe2+

II

III

form II predominates for this diamagnetic compound. magnetic coupling between the Fe

III

150

Strong

centres occurs via the bridge

sulphur atoms.. Possible relationships to structures of ferredoxins with two irons and two labile sulphurs are-discussed;

Although the

complex anion pe4S4(SR)4]27 1s not- an organometallic derivative, the paper

151 .-describing this structure;includes a comparison of other

tetranuclear cluster systems with.a cubane-type structure, of which many organometallic examples have now been described.

It is of

interest tliat~the Fe S (SR) core : 44 4

is an analogue

Of clostridial Fe-S proteins

also the description--of com+lex (28)].

bee

of

the active

sites

Ferrocene

and

benchrotrene The

ButCl be

in the

the

have

tetra-t-butylferrocene

presence

respectively

in the

product.

and

the rotation

two

independent

diene

adds

ions

153

That

C5 rings

eclipsed

to the

relieve of

of

the

is

the

15 and

and

(6x+4x)

to

18O addition

cycle-

a single structure

suggests

152.

rings

Stereospecific gives

’

and

shown

strain,

rings

unit,

(136),

that

the

manner. and

synthesis

ferrocene been

FcCMe2 + has

from

in a formal

details

the

ferrocene

has

steric

molecules.

obtained

from

mixture

to cyclopentadiene

in the

cation

Full

To

(135).

of ferrocenylcarbonium addition

obtained

of an AlC13-LiAlH4

l,l', 3,3'-isomer

a 7O dihedral,

with

derivatives

structure

of

(s,g,S)-

2-(~-methoxyphenyl)hydroxymethyl-N,N-dimethyl-l-ferrocenylethylamine (137).are result

reported,

enables

and

as mentioned

previousl;-

structure

assignments

unequivocal

[AS 72/l; for

1681,

a large

this

number

of

wl-(_ c---\

_’

4

:

:

Te I

,/-;

‘,_-d

(136)

(135)

optically

active

ferrocene

A complete [l.l]ferrocenophane appeared midway

in 1967. between

configuration References

P. 385

discussion

(138) 156

derivatives

has

In this

the eclipsed of

the bridged

been

of

to be made. the

given

staggered

ferrocene

155 the

molecule,

and

structure ;

of

1,12-dimethyl-

a preliminary

angles

positions.

alcohol

154

of

twist The

account lie

almost

relative

([3]ferrocenophanol)

(1391,

Me (138) Ph I

(139)

m-p. 122O, has been determined, IWIR methods.

157

and is the same as that predicted by

The molecular struc:ure of the bridged ferrocenyl ketone

(140) has been illustrated, but no other details are yet available- 158 An ionic complex, obtained from FcAuPPh3 and HBF4. with the composition

[PcAu2(PPh3)2]BP4. has the unusual structure <141), in

which the metal atoms from an Fe-Au-Au chain. 159

The two gold atoms

are bridged by one carbon of a cyclopentadienyl group, and this coaqlex is also the first structurally characterised example of a ferrocene derivative with a direct Fe-M bond.

Ph

381 Me \

Me 0 (143) Carbonyl groups

C-112)

The between been

o_hydroxy-

two

the acetyl also

to the

and

a Dzd

faces.

tetrahedron

which

phosphine

161

triphosphine

The

The

while

and

of

the hydroxyl

group. the

has

In particular,

in the methoxy

the alkoxy

143)

derivative,

The

Cr(C0)3

group

projections groups

unusual

metal-ligand four

salt

The contains

Raferencesp.385

hydride

hydride

H4Mo(PMePh214

coordination

sphere

ligands

the flattened

form

(144)

with

an elongated

tetrahedron

temperature-dependent

complex obtained

in the presence

hydrogens,

nonrigid

'l-land

formed 31P

NMR

by

the

spectra

structure.

h as been

fluorophosphate

3'

with

reactions

complexes

penetrates

to the

MeC(CH2PPh2)J

PPh

(142

structures.

orientation

stereochemically

The

and

from

in the

related

ligands.

related

three

their

oxygen,

away

dodecahedral

triangular

by

acetyl

points

The

are

in some

to acetyl).

hydrides

contains

of

"quasienantiomeric'.',

a difference

(relative

stereoselectivity

the basis

are

oxygen

show

Metal

on

complexes

hydrogen-bonded

of

and z-methoxyacetylbenchrotrenes

160

expiained

the

difference

omitted

is sho& and

hydride the

also

cation from

of NaBH4.

(145). joined

iron(X)

162 The

by

RuH2(PPhi)4, four

[Fe2H3(triphos)2]+

phosphines

The two

halides

atoms

a metal-metal obtained

and

structure iron

from

[triphos

bond

=

the

of

the

hexa-

are.bridged (2.342).

Ru(CgHg)(CGH8)

arranged-approximately.tetra-

P P = PMePhZ

P

G

MeC(CHgPh213

P U44)

(14%

hedrally about the metal

bngles

(1461

163

P-Ru-P, 104.2-116.4(2)"].

Although

the hydrogen atoms were not located, the H-Ru-H angle is calculated at.98O. !&a rutfienium

coordination

in trans-auH,CPPh(O~t)~]~

(146)

consists

a flattened RuP4 tetrahedron, with axial hydride ligands, which however, is much closer to octahedral than found in c&-FeHa@Ph2(OEt)2]4, which is closer~to tetrahedral. larger Ru

11

164

These differences are related to the

radius, and the larger number of P-M-P 90° angles in

idealised cis (5) than in trans (4).

,

The strong trans-influence of hydrogen is indicated in the

structure of trans-PdHCl(PEt312, where the Pd-Cl bond length is 2.427(5)2 (cf. PdC142-, 2.299:; An X-ray diffraction study

166

sum of covalent radii, 2.3O$.165

of U(BH4)4

(147) revealed a polymeric

structure made up of interlocking helical chains in which a fourfold .screw axis relates individual units. six BH4.groups

(four bridging,

Each uranium atom is linked to

two terminal).

further elucidated by a neutron-diffraction hydrogens to be located.

167

The structure has been

study, which enabled the

Four BH4 groups are attached via two

hydrogens to one.metal atom, bridging neighbouring uraniums with the others.

The

other two (cis) BH4 groups are attached by three hydrogens,

r&sulting.in.an overall coordination number of 14 for the uranium atom;

d capped h&&onal:antiprism

is the ideal reference-polyhedron.

Comparisons.with -other M-BH4 complexes show, that the M-B- distance can becorrelated

with .the mode of attachment- of:the BH4_group.

of

383

In (~J~-C,H,)~T~BH~ (148), coordination of the tetrahydroborate group occurs via bridging hydrogen atoms, as found in (Ph3P)2CuBH4. and with which comparison is made.

168

Disorder was found in the C5 rings.

Nitrosyls Recent structural results on metal-nitrosyl

complexes have disclosed the

existence of two types, in which the M-N-O moiety is either linear or bent.

These observations have been correlated with coordination of

nitric oxide as NO+ or NO-, respectively.

In the complexes CoC12(CO)L2

(L = tertiary phosphine), IR, NMR, and X-ray photoelectron 169 suggest the existence of conformational isomers.. trigonal-bipyramidal

spectra

One (A) has

geometry with a linear NO group, while the second

(B) is thought to be square-pyramidal, with a bent NO at the apex.

The

structure of C0C13(N0)(PMePh2)3, (149) reveals a distorted trigonal bipyramid, with no evidence forisomer B.

An extended discussion on the

scope and limitations of the various spectroscopic methods.fails

to

conclusively resolve this bent vs. linear nitrosyl situation, and further experiments are needed to clarify the earlier results which indicated the existence of a dynamic intramolecular redox equilibrium. The nitrosyl Mo(NOXSRCNBu$9 bipyramidal coordination an axial position. ReferencesP.385

170

(150) has pentagonal

about molybdenum, with an NO group occupying

The latter is almost linear [angle MO-N-O,

+ 173.2<7)OJ, indicating coordination as NO . The compound previously described as (NH4)2[~u(~~)~14(OH)] on the basis of an electron density projection have the.composition

octahedral complex anion

.I

/-

-H--_, ,A

via O-E---Cl

hydrogen

bonds

(151).

P

P

/Cl

with an

The chloride ions are attached to the

//\ b

-0--&

In

172

P-Ru-

’

C’:___HJ-ft

has been shown to

(NH~)~[Ru(NO)C~~(H~O)]-C~-H~O,

almost linear Ru-N-O group.

.-n

171

p\

[Ru (NW (dppe) 2]BPh4 (152),

i

the equatorial NO group is

linear, corresponding to a formally c8 Rue complex of NO+. picture of the.bonding of NO to metals in five-cokdinate also discussed.

173

envir&&nt

complexes is

Comparisons of the structures of the nitrosyl

[~C~L(NO)]~~PF6) with P_l&(&i~CA2~2pph2j>

An MO

the parent

cotiplen [ahc~.L] CL =

have deen made.174

Minimal

.occur,' and the- sixtlipotential

changes in the RhL

site.is crowded;

in both

385 cokplexes, linkage sense

all

three

is bent

D31(1)OJ,

and

are

coordinated.

is interpreted

The

Rh-NO

as coordination-in.the.

acid.

details

of

the

structure

of Pt4(0Ac)6(N0)2

have

been

175

published;

the

In this

two Pt-Pt

tetramer

complex

distances

interaction

been

a study

isomers, 176

of a bent of

true-nitrosyl hyponitrite

the nitrosyl

in the

prepared.

the presence

is solvated

r3.311

occurs Two

and

atoms

RhI'fNO-. Full

have

phosphorus

the mixed complex,

group

and

with

grqup

2.944;(1

is formulated

suggest

shorter

separation.

red

black,

and

of

The

structure

of

Co-N-O

group

(12OO).

that

the

in the manner:

that

the

The

salt

two

of acetic

as NO-.

The

a metal-metal

[CO(NH~)~(NO)]~~

the black

bromide-nitrate

but

two molecules

chloride

red

shows

isomer that

cobal- L atoms

are

cation

revealed is binuclear,

it is not bridged

a

by a

177

Co-0-N-N(O)-Co.

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