Metal core rearrangements in hetero-bimetallic nona-osmium carbonyl clusters; the crystal and molecular structures of [Os9(CO)24{Au(PCy3i)}2] and [Os9(CO)23(Au2DPPE)]

DOI: 10.1016/S0022-328X(97)00188-5

Source and publish data:

Journal of Organometallic Chemistry p. 131 - 139 (1998)

Update date:2022-07-30

Topics:

Authors:

Akhter, Zareen

Ingham, Scott L.

Lewis, Jack

Raithby, Paul R.

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Article abstract of DOI:10.1016/S0022-328X(97)00188-5

The reaction of the nona-osmium cluster dianion [(Ph₃P)₂N]₂[Os₉(CO)₂₄] with the electrophilic gold reagents AuPR⁺₃ and Au₂L²⁺ (where R = Ph (2a, 3a), Cy (2b, 3b) and L = bis-(diphenylphosphino)methane (DPPM) (1a) or 1,2-bis-(diphenyl)ethane (DPPE) (1b)) has been studied. The monogold fragment reacts to give both the mono- and di-substituted products [(Ph₃P)₂N][Os₉(CO)₂₄{Au(PR ₃)}₂] and [Os₉(CO)₂₄{Au(PR₃)}₂]. The structure of the latter cluster (R = Cy (2b)) has been determined by a single crystal X-ray diffraction analysis and a major rearrangement of the metal core geometry was found to have occurred on coordination of the gold fragments. In contrast, reaction with the digold reagent Au₂L₂₊ results in the isolation of only one product of formulation [Os₉(CO)₂₃(Au₂L)], where coordination of the heteroatom moiety has been accompanied with the loss of a carbonyl ligand. From a single crystal X-ray diffraction analysis (L = DPPE (1b)) this compound was shown to have retained its original cluster geometry, with the gold atoms coordinated in close proximity to each other.

Full text of DOI:10.1016/S0022-328X(97)00188-5

Journal of Organometallic Chemistry 550 1998 131–139

Metal core rearrangements in hetero-bimetallic nona-osmium carbonyl

ž / /5₂x

clusters; the crystal and molecular structures of Os₉CO ₂₄Au PCy₃

ž / ž /x

and Os₉CO ₂₃Au₂DPPE

)

Zareen Akhter, Scott L. Ingham, Jack Lewis, Paul R. Raithby

Department of Chemistry, Lensfield Road, Cambridge CB2 1EW, UK

Received 29 January 1997

Abstract

wŽ

x w

₂₄x

The reaction of the nona-osmium cluster dianion Ph₃P ₂N Os₉CO

with the electrophilic gold reagents ‘‘AuPR^q₃’’ and

. Ž

‘‘Au₂L²’’ where RsPh 2a, 3a , Cy 2b, 3b and Lsbis- diphenylphosphino methane DPPM 1a or 1,2-bis- diphenyl ethane

DPPE

wŽ

has been studied. The monogold fragment reacts to give both the mono- and di-substituted products

. Ä .4x . Ä .4 x ..

Ph₃P ₂N Os₉CO ₂₄Au PR₃and Os₉CO ₂₄Au PR₃. The structure of the latter cluster RsCy 2b has been determined by a

single crystal X-ray diffraction analysis and a major rearrangement of the metal core geometry was found to have occurred on

coordination of the gold fragments. In contrast, reaction with the digold reagent ‘‘Au₂L²^q’’ results in the isolation of only one product of

. Ž

formulation Os₉CO Au₂L , where coordination of the heteroatom moiety has been accompanied with the loss of a carbonyl ligand.

From a single crystal X-ray diffraction analysis LsDPPE 1b this compound was shown to have retained its original cluster geometry,

with the gold atoms coordinated in close proximity to each other. q 1998 Elsevier Science S.A.

Keywords: Osmium; Gold; Cluster carbonyls; X-ray structure; Phosphines

w x

1. Introduction

bonding 2 . The synthesis of many of these compounds

has been achieved by the use of redox condensation

reactions between anionic carbonyl compounds and neu-

tral or cationic metal electrophiles, with the use of

mercury and gold fragments being particularly success-

There has been considerable interest in synthesis of

hetero-bimetallic compounds because of the polarity

that the heterometallic bond introduces to the molecule.

This polarity difference may enhance any electrochemi-

cal or photochemical reactivity that the molecule pos-

w x

ful 3 .

The number of high nuclearity metal-carbonyl clus-

w x

sesses 1 and, as such, hetero-bimetallic compounds are

ters that have been structurally characterised has steadily

increased in recent years. It has been observed that

many of these compounds no longer obey the classical

electron counting rules which have been so widely

employed to rationalise the structures of their lower

of interest due to their possible applications in materials

science. Large polynuclear metal-carbonyl clusters also

exhibit unusual physicochemical properties due to the

relationship between electronic delocalisation and the

number of metal atoms within the cluster. Therefore, it

is not surprising that in recent years there has been an

increasing collection of compounds synthesised which

are comprised of a large polynuclear metal-carbonyl

cluster and incorporate some degree of hetero-bimetallic

w x

nuclearity counterparts 4 . This apparent breakdown in

the electron counting rules reflects the delocalised elec-

tronic nature within the metal framework. As such, the

metal–metal interaction within these species may be

thought to lie at the interface between the localised

bonding involved in classical organometallic com-

pounds and the high electron mobility that is an intrinsic

property of metallic solids. A consequence of the in-

creasing electron delocalisation within high nuclearity

metal-carbonyl clusters is that the metal–metal bonding

)

Corresponding author.

¹Dedicated to Professor Ken Wade on the occasion of his 65th

birthday in recognition of his outstanding contributions to

organometallic and inorganic chemistry.

0022-328X

(

)

132

Z. Akhter et al.rJournal of Organometallic Chemistry 550 1998 131–139

DPPE in the presence of the halide abstractor TlPF₆

may be thought to consist of a significant proportion of

s-character and, as such, has considerably more direc-

tional flexibility. As a result of this increased flexibility

within the metal core, the introduction of a heterometal-

lic fragment may perturb the cluster framework, either

as a consequence of the formation of the new polar

metal–metal bond, or arising from the steric constraints

of the incoming group.

to give, after purification, a brown neutral cluster com-

pound as the only isolable product. On the basis of

spectroscopic data the cluster has been formulated as

. Ž

ŽŽ

Os₉CO Au₂L

1a LsDPPM, 1b LsDPPE ,

where not only has coordination of the digold fragment

occurred, but a carbonyl ligand has been ejected from

the cluster. In contrast, two brown products were iso-

lated when the reaction was performed using the mono-

w x

We have recently shown 5 that the reaction between

x w ₂₂x

. Ž

the anionic cluster Ph₃P N Os₈CO

and gold

gold electrophilic reagent AuPR₃NO where RsPh,

electrophilic fragments results in a subtle balance be-

tween the kinetically and thermodynamically favoured

products. It was noted that the thermodynamic product

resulted in a significant metal core rearrangement and

that this transformation proceeded smoothly at ambient

temperatures. However, it was observed that the kinetic

product could be stabilised and isolated by the use of a

digold fragment linked with a bidentate phosphine. In

an attempt to further explore this unusual reactivity and

to investigate what effect increasing cluster size may

have upon it, we now report the results of a study of the

interactions between the high nuclearity cluster dianion

Cy . From the chromatographic properties and the spec-

troscopic data of these compounds, one has been identi-

fied as the neutral cluster Os₉CO Au PR₃

4₂

ŽŽ

RsPh, 2b RsCy , whilst the other product has been

wŽ

formulated as the anionic cluster Ph₃P N Os₉CO

ŽŽ

Ä^{1 24}4

Au PR₃

3a RsPh, 3b RsCy . The P H

NMR spectra of the compounds 1a and 1b exhibit

two resonances of equal intensity, indicating that the

gold atoms are in non-equivalent environments and that

these sites do not exchange to any significant degree on

the NMR time scale at room temperature. In contrast,

only one resonance was observed in the P H NMR

spectra of 2a and 2b , implying that either the two

gold atoms were coordinated in equivalent sites or they

were rapidly exchanging. For the anionic compounds

Ä¹

x w

x w x

6 and selected electrophilic

Ph₃P N Os₉CO

gold reagents.

3a and 3b two resonances are observed with a ratio

of 2:1, the more intense peak being attributable to the

wŽ

x^q

cation Ph₃P N .

2. Results and discussion

CH Cl₂solution of the cluster dianion

x²w

x w x

reacts with the digold

. Ž .x

The molecular structure of Os₉CO Au₂DPPE

Ph₃P N Os₉CO

1b has been determined by a single crystal X-ray

reagent Au₂Cl₂L where Lsbis- diphenylphosphino -

Ž .

diffraction analysis Fig. 1 and selected bond lengths

methane DPPM or 1,2-bis- diphenylphosphino ethane

.4x Ž

Fig. 1. Diagram depicting molecular structure of Os₉CO Au₂DPPE 1b .

(

)

Z. Akhter et al.rJournal of Organometallic Chemistry 550 1998 131–139

133

Table 1

are presented in Table 1. The central metal geometry

Ž .

.4x Ž .

Selected bond lengths A for Os₉CO Au₂DPPE

may be described as a tricapped octahedron of osmium

atoms, with one of the gold atoms also capping an

octahedral face and the remaining gold atom bridging

between the octahedron and a capping osmium atom,

Ž . Ž .

Au 1 –P 1

Ž .

Ž . Ž .

Ž .

2.752 2

2.318 10

2.819 2

2.826 2

Os 2 –Os 9

Os 2 –Os 5

Os 2 –Os 3

Ž .

2.755 2

Au 1 –Os 1

Ž . Ž .

Ž .

2.780 2

Au 1 –Os 3

Ž . Ž .

Ž .

2.859 2

Au 1 –Au 2

2.837 2

Ž .

Os 2 –Os 8

Ž . Ž .

adopting the asymmetric m₃m₂bonding mode Fig. 2 .

Ž .

2.802 2

Au 1 –Os 4

2.923 2

Os 3 –Os 8

Ž . Ž .

Ž .

2.879 2

The osmium–osmium bond lengths vary quite dramati-

Au 2 –P 2

2.275 9

2.719 2

Os 3 –Os 5

Ž .

Ž . Ž .

Ž .

3.035 2

Au 2 –Os 3

Os 3 –Os 4

Ž .

cally within the cluster, ranging from 2.605 2 for

Ž . Ž .

Ž .

2.778 2

Au 2 –Os 5

2.874 2

Ž .

Os 4 –Os 9

Ž . Ž .

Ž .

Os 1 –Os 3 to 3.035 2 A for Os 3 –Os 4 and having

an average value of 2.82 A. The general trend within

Ž . Ž .

Ž .

2.945 2

Os 1 –Os 3

Ž . Ž .

2.605 2

Os 4 –Os 6

Ž . Ž .

Ž .

2.970 2

Os 1 –Os 9

Ž . Ž .

2.753 2

2.784 2

Os 4 –Os 8

this distribution of distances is that the osmium atoms

with the highest metal–metal connectivity are associ-

ated with the shortest bond lengths, but there are several

significant exceptions to this trend, notably in bonds to

Ž .

Ž . Ž .

Ž .

2.685 2

Os 1 –Os 5

Os 6 –Os 9

Ž . Ž .

Ž .

2.762 2

Os 1 –Os 6

2.812 2

Ž .

Os 7 –Os 9

Ž . Ž .

Ž .

2.936 2

Os 1 –Os 2

Ž . Ž .

2.866 2

Os 7 –Os 8

Ž . Ž .

Os 8 –Os 9

Ž .

2.839 2

Os 1 –Os 4

Ž . Ž .

2.902 2

Ž .

2.721 2

Os 2 –Os 7

Ž .

Os 4 . The gold atoms form interactions with the os-

Ž .

mium centres ranging from 2.719 2 –2.923 2 A, mak-

Ž .

ing the shortest bonds to Os 1 and Os 3 , which them-

selves have the highest metal–metal connectivity. The

possesses a tricapped octahedral metal geometry. Whilst

there appears to be no obvious correlation of the

metal–metal distances between the three clusters, the

average osmium–osmium bond lengths in 4 and 5 of

2.86 and 2.84 A respectively, are not dissimilar to that

of 2.82 A observed for 1b . Indeed the average os-

mium–gold distance of 2.85 A found in the cluster 4 is

in accord with a value of 2.83 A for 1b . It is notewor-

thy that the osmium–osmium bond lengths for 1b

Ž .

two gold atoms are at a distance of 2.837 2 A from one

another, hence there is the possibility of a significant

bonding interaction between them. This variability of

bond distances seems to be a feature of many high

nuclearity metal clusters; this may be a consequence of

the greater flexibility within the metal framework, due

to less stringent directional constraints on metal–metal

interactions as a result of increased electron delocalisa-

tion, or because there is a significant contribution of

‘metal character’ into the cluster bonding. The observed

Ž .

show a greater variation than for those observed for

Ž .

both 4 and 5 and may possibly be due to the steric

geometry for 1b is remarkably similar to that reported

5 for the octaosmium cluster Os₈CO Au₂DPPB

4 , except that an additional face of the octahedron has

requirements of the digold moiety and the increased

flexibility within the metal framework of 1b .

w x . Ž

Ž .

The solid-state m olecular structure of

Os₉CO Au PCy₃

4₂

been capped by an Os CO unit. In addition, the

2b has also been determined

tricapped octahedral osmium metal core of 1b is the

by X-ray crystallography Fig. 3 and selected bond

lengths are presented in Table 2. The observed geome-

try of the osmium core is best described as a bicapped

octahedron of osmium atoms, where an edge of the

same geometry as that observed for the related cluster

x w x Ž .

5 , and although the

Ph₃P N Os₉H CO

structure of the precursor dianionic cluster

x w ₂₄x Ž .

Ž .

Ph₃P N Os₉CO 6 has not been determined

octahedron is bridged by a further osmium atom Os 9

experimentally, there is good evidence that it is also

Fig. 4 . The two gold atoms may be thought to cap the

.4x Ž

Fig. 2. Diagram depicting metal core geometry of Os₉CO Au₂DPPE 1b .

(

)

134

Z. Akhter et al.rJournal of Organometallic Chemistry 550 1998 131–139

Table 2

opposite sides of the pseudo Os₄‘butterfly’ described

Ž .

.4 x Ž

Selected bond lengths A for Os₉CO Au PCy₃

Ž .

by the atoms Os 3 , Os 5 , Os 7 and Os 9 , and with

Ž .

2.694 3

2.940 2

2.918 2

2.965 3

2.877 4

2.738 4

2.867 4

2.738 3

2.793 2

2.816 2

2.974 2

3.029 2

Ž .

Ž . Ž .

Ž .

Os 1 –Os 2

Os 4 –Os 6

Os 4 –Os 8

Os 5 –Os 7

2.861 2

2.874 5

2.870 2

Ž .

2.926 4

2.779 2

Ž .

2.784 2

2.849 2

Ž .

2.859 4

2.916 4

Ž .

2.777 2

2.807 2

Ž .

2.907 2

2.978 2

the gold atoms separated by a distance of 4.68 A it is

Ž .

Os 1 –Os 4

unlikely that there is any significant bonding interaction

between them. The osmium–osmium bond lengths

Ž . Ž .

Ž .

Os 1 –Os 6

Ž . Ž .

Ž .

Os 2 –Os 3

Ž . Ž .

Os 5 –Os 8

Ž . Ž .

Ž .

within the cluster range from 2.694 3 to 2.965 3 A and

Ž .

Os 2 –Os 4

Ž . Ž .

Os 5 –Os 9

Ž . Ž .

Ž .

have an average value of 2.85 A. The observed cluster

geometry is similar to that reported 7 for the related

Os 2 –Os 5

Os 5 –Au 2

Ž . Ž .

Ž .

Ž . Ž .

Ž .

Os 2 –Os 6

Os 6 –Os 7

w x

Ž . Ž .

Ž .

Os 2 –Os 7

Ž . Ž .

Os 6 –Os 8

Ž . Ž .

.4₂x

Ž .

octaosmium digold cluster Os₈CO Au PPh₃7 ,

Ž .

Os 3 –Os 5

Ž . Ž .

Os 7 –Os 8

Ž . Ž .

where the osmium metal geometry was described as an

octahedron with one edge bridged by two more osmium

atoms. Although there are similarities in the gross over-

Ž .

Os 3 –Os 7

Os 7 –Os 9

Ž . Ž .

Ž .

Ž . Ž .

Ž .

Os 3 –Au 1

Os 7 –Au 1

Ž . Ž .

Ž .

Os 3 –Au 2

Ž . Ž .

Os 9 –Au 1

Ž . Ž .

Ž .

Os 4 –Os 5

2.846 2

Os 9 –Au 2

Ž .

all metal framework between the clusters 2b and 7 ,

there are several distinctive differences between the two

structures. These differences are most pronounced for

the so-called ‘wing-tip’ atoms of the pseudo Os₄‘but-

Ž .

terfly’, which are separated by 3.373 3 A in 7 , whereas

in 2b they are significantly closer at 3.224 3 A. In

addition, for 7 , these atoms are thought not to interact

The observed molecular geometries of 1b and 2b

are in agreement with the spectroscopic data, which

indicated the coordination of the two gold atoms in

non-equivalent environments for 1a and 1b , whereas

both gold atoms were thought to be bound in equivalent

sites for 2a and 2b . From these results it seems

reasonable to assume that the geometries of the clusters,

as determined in the solid state, are retained to a

significant degree in solution.

There appears to be a clear similarity in the reactivity

of the octa- and nona-osmium dianionic clusters

Ž .

to any significant degree with the apical osmium atoms

Ž .

of the octahedron, being at a distance of 3.142 3 and

Ž .

3.108 3 A from them. Contrasting this for 2b , one

apex of the octahedron is bound to a ‘wing-tip’ osmium

Ž . .

Ž .

atom Os 2 –Os 3 ; 2.965 3 A , whereas the other pair

Ž . Ž ..

of atoms Os 8 , Os 9 are separated by a distance of

3.391 3 A and, as such, it is unlikely that any bonding

interaction exists between them. From the overall

molecular structure observed for 2b , it is apparent that

a major reorganisation of the cluster’s metal framework

has occurred from that of the tricapped octahedral ge-

Ž .

x w

₂₂x Ž .

x w

Ph₃P N Os₈CO

and

Ph₃P N Os₉-

₂₄x²Ž .

towards gold electrophilic reagents. For

both compounds, reaction with mononuclear gold frag-

ments results in the formation of a cluster in which a

substantial metal core rearrangement has occurred,

wŽ

ometry of the precursor dianionic cluster Ph₃P N -

x w x

6 .

Os₉CO

.4 x Ž

Fig. 3. Diagram depicting molecular structure of Os₉CO Au PCy₃

2b .

(

)

Z. Akhter et al.rJournal of Organometallic Chemistry 550 1998 131–139

135

.4 x Ž

Fig. 4. Diagram depicting metal core geometry of Os₉CO Au PCy₃

2b .

whereas reaction with a digold reagent where the gold

the cluster after the initial coordination. Although no

evidence was obtained which could be used to unam-

biguously assign the structures of the mono-substituted

centres are connected with a bidentate phosphine re-

sults in the formation of a product where the osmium

metal framework remains identical to that of the starting

material. The exact reasons why such a reactivity differ-

ence exists remain unclear; however, we have shown

previously that when mononuclear gold fragments react

with the octaosmium cluster 8 a kinetically favoured

product is initially formed and that this rearranges to

give 7 , which may be thought of as the thermodynam-

ically favoured product. No evidence of the formation

of an intermediate product was observed for the analo-

gous nona-osmium compound; however, it is feasible

that rearrangement of the larger cluster is more facile

and that reorganisation occurs rapidly at ambient tem-

peratures. Another important factor to take into consid-

clusters 3a and 3b , it seems likely that these will

have a tricapped octahedral geometry.

The formal electron count for compound 1b is 120;

however, if it is assumed that the cluster consists of a

tricapped octahedron, then this has an electron count of

122 predicted from the ‘polyhedral skeletal electron pair

Ž .

w x

theory’ for condensed polyhedra 8 . In comparison,

2b has an observed electron count of 122 and, if the

osmium framework is described as a bicapped octahe-

dron with a further edge bridged, then the predicted

electron count is 124 as determined by the condensed

polyhedron method. However, if a bonding interaction

Ž .

is assumed between Os 3 and Os 9 , or indeed between

Ž .

eration, is that when 6 reacts with the digold reagent

Os 8 and Os 9 , then a predicted count of 122 electrons

is obtained using this method.

‘‘Au₂L^2q’’ a carbonyl ligand is lost, whereas no re-

moval of a carbonyl group was observed for the reac-

Ž .

tion with 8 . This is probably due to the greater steric

crowding that occurs between the ligands at the cluster

surface as the number of metal atoms increases. How-

ever, the possibility that the reaction is proceeding via a

different pathway for the larger cluster may not be

entirely discounted. Another important difference in the

reactivity between the octa- and nona-osmium clusters,

is that a monoanionic product is formed in the reaction

3. Experimental

All reactions were performed under an atmosphere of

purified dinitrogen by standard Schlenk and vacuum

w x

line techniques 9 . Subsequent work-up of products

was carried out without precautions to exclude air.

Solvents used were distilled from appropriate drying

agents under dinitrogen. Routine separations of products

were performed by thin layer chromatography using

commercially prepared glass plates, precoated to

0.25 mm thickness with Merck Kieselgel 60 PF₂₅₄, or

using laboratory-prepared glass plates coated to 1 mm

Ž .

between 6 and the mononuclear gold electrophiles,

Ž .

whereas no analogous compound was isolated for 8 .

The formation of this anionic product may be ratio-

nalised in terms of the relative charge density on the

cluster after coordination of the first gold fragment.

Whilst both the mono-substituted octa- and nona-

osmium compounds would carry a negative charge, this

would be delocalised to a greater extent on the larger

cluster, deactivating it to some extent towards further

reaction with the electrophilic gold reagent. This appar-

ent deactivation of the cluster is not observed when the

reaction is performed using the digold fragments, with

the second gold atom being held in close proximity to

thickness with Merck Kieselgel 60 PF₂₅₄

IR spectra were recorded as dichloromethane solu-

tions on a Perkin–Elmer 1710 Fourier transform spec-

Ä¹

trometer. H and P H NMR spectra were recorded

on a Bruker AM-400 spectrometer and were referenced

to external tetramethylsilane and trimethylphosphite re-

spectively. Mass spectral data were obtained by the

method of liquid secondary ion mass spectrometry

(

)

136

Z. Akhter et al.rJournal of Organometallic Chemistry 550 1998 131–139

LSIMS on a Kratos MS-50 mass spectrometer, using

m-nitrobenzylalcohol as a matrix. Elemental analyses

were performed in this department by standard tech-

CDCl₃: d y46.7 s, 1P , y119.9 s, 2P . H NMR

. Ž

ppm, CDCl₃: d 7.38–7.71 m, 45H ; 2b : IR n_CO

Ž .

CH₂Cl₂: 2091m, 2061s, 2048 sh , 2040vs, 2009 sh ,

1999m, 1969w br cm^y1. Positive ion LSIMS mass

x w . x

Ph₃P N Os₉CO ,

niques. The compounds

Au PR₃NO₃where RsPh, Cy and Au₂Cl₂L where

spectrum: mrz 3351 observed , 3354 calculated, based

. 4 Ž . Ž

Ä¹

192

LsDPPM, DPPE were prepared according to litera-

Os . P H NMR ppm, CDCl₃: d y55.9 s,

ture procedures 6,10,11 .

2P . H NMR ppm, CDCl₃: d 1.46–1.88 m, 66H ;

3b : IR n_COCH₂Cl₂: 2082w, 2049vs, 2039vs,

2018m, 1987m br cm^y1. Negative ion LSIMS mass

[

(

) (

)] (

3.1. Preparation of Os₉CO ₂₃Au₂L

DPPM 1a , DPPE 1b

where Ls

₂₄x

(

)

(

))

spectrum: mrz 2878 observed , 2877 calculated, based

. 4 Ž . Ž

Ä¹

Os . P H NMR ppm, CDCl₃: d y70.0 s,

192

x w

50 mg,

To a solution of Ph₃P N Os₉CO

1P , y119.9 s, 2P . H NMR ppm, CDCl₃: d 1.41–

15mmol in 25 ml of dichloromethane were added one

equivalent of Au₂Cl₂L and an excess of the halide

abstractor TlPF₆. The mixture was stirred at room tem-

perature for 30 min, the solvent was removed and the

residue purified by thin layer chromatography, eluting

with a 60% CH₂Cl₂–n-hexane mixture to give the

desired product in approximately 65% yield.

1.85 m, 33H , 7.34–7.64 m, 30H .

[

(

)

3.3. Crystal structure determination for Os₉CO ₂₃

)] (

(

)

Au₂DPPE 1b

Os₉Au₂P₂O₂₃C₄₉H₂₄, orthorhombic, space group

Ž .

Pna2₁, as29.552 6 , bs16.867 4 , cs15.108 3 A,

Ž .

Spectroscopic data for 1a : IR n_COCH₂Cl₂:

Us7531 3 A , Zs4, F 000 s5496, m Mo Ka s

19.097 mm^y1

D_cs2.777 g cm^y3. A brown block-

Ž .

2092m, 2066m, 2050vs, 2026 sh , 2012m, 2001w sh ,

1936w br cm^y1. Positive ion LSIMS mass spectrum:

shaped crystal of approximate dimensions 0.15=0.20

=0.20 mm³was mounted on a glass fibre, D_mnot

recorded, accurate lattice parameters determined from

192

mrz 3146 observed , 3150 calculated, based on Os .

Ä¹

P H NMR ppm, CDCl₃: d y71.4 d, 1P , y100.3

d, 1P J PP s72.9 Hz. ¹H NMR ppm, CDCl₃:

25 reflections us15.10–16.898 . Intensity data were

measured on a Rigaku AFC7R diffractometer using

monochromated Mo Ka radiation and v scan mode to

a maximum value for u of 22.58. Three standard reflec-

tions were monitored after every 100 reflections col-

lected and showed an average decrease in standard

intensity during the data collection time of y65%; a

linear decay correction was applied to compensate for

this apparent decay of X-ray intensity. A total of 7816

reflections were measured within the range y21FhF

. Ž

d 3.57–4.12 m, 2H , 7.31–7.75 m, 10H ; 1b : IR n_CO

Ž .

CH₂Cl₂: 2091m, 2066m, 2049vs, 2026 sh , 2011m,

2001w sh , 1995w br cm^y1. Positive ion LSIMS mass

Ž .

spectrum: mrz 3159 observed , 3164 calculated, based

192

Ä¹

on Os . P H NMR ppm, CDCl₃: d y60.12 s,

1P , y92.0 s, 1P . H NMR ppm, CDCl₃: d 2.48–

3.35 m, 4H , 7.41–7.72 m, 10H .

[

(

) ( ) ] (

3.2. Preparation of Os₉CO ₂₄AuPR₃

Ph 2a , Cy 2b and Ph₃P ₂N Os₉CO ₂₄AuPR₃

(

where Rs

(

)

(

))

[(

)

][

(

) (

)]

31, y13FkF18, y16FlF16 and averaged Friedel

(

)

(

))

where RsPh 3a , Cy 3b

opposites not merged to yield 7150 unique reflections

R_ints0.0532 of which 5464 were judged as signifi-

x w .₂₄x Ž

To a solution of Ph₃P N Os₉CO 50 mg,

cant by the criterion that F_obs)4s F_obs. Corrections

for Lorentz and polarisation effects were applied. Ab-

sorption corrections was applied using the method of

15mmol in 25 ml of dichloromethane was added an

excess of Au PR₃NO₃. The mixture was stirred at

room temperature for 3 h, the solvent was removed and

the residue purified by thin layer chromatography, elut-

ing with a 60% CH₂Cl₂–n-hexane. In order of elution

the neutral cluster compound 2a and 2b was ob-

tained in 60% yield, whilst the mono-anionic product

ŽŽ

Walker and Stuart 12 , minimum and maximum correc-

tions 0.719 and 1.220 respectively. Structure solution

was by a combination of direct methods and Fourier

techniques. Refinement of the ‘Flack parameter’ 13 to

a value of y0.01 2 indicated that the correct absolute

ŽŽ

Ž .

3b and 3b was isolated in a yield of 25%.

Spectroscopic data for 2a : IR n_COCH₂Cl₂:

configuration had been assigned. Anisotropic thermal

motion was assumed for the osmium, gold and phos-

phorus atoms. Hydrogen atoms were placed in calcu-

lated positions and refined using a riding model. Full

matrix least squares refinement on F_o²_bsfor 7150 data

Ž .

2092m, 2064s, 2050 sh , 2042vs, 2013 sh , 2001m,

1954w br cm^y1. Positive ion LSIMS mass spectrum:

192

mrz 3314 observed , 3318 calculated, based on Os .

P H NMR ppm, CDCl₃: d y65.8 s, 2P . ¹H

Ä¹

and 405 parameters converged to wR2s0.1169 all

. Ž

NMR ppm, CDCl₃: d 7.32–7.67 m, 30H ; 3a : IR

data , conventional Rs0.0509 observed data , GOF

n_COCH₂Cl₂: 2084w, 2049vs, 2039vs, 2019m,

all data s1.031. The function minimised was Ýw F

1988s br , 1972 sh , 1936w sh cm^y1. Negative ion

y F², w s 1r s F_obsq 0.0437P q 88.06P

²Ž

^obx^s

Ž .

calc

where Ps F_obsq2F²r3 and s was obtained from

LSIMS mass spectrum: mrz 2855 observed , 2859

calc

192

. 4 Ž

Ä¹

calculated, based on

Os . P H NMR ppm,

counting statistics.

(

)

Z. Akhter et al.rJournal of Organometallic Chemistry 550 1998 131–139

137

[

(

)

3.4. Crystal structure determination for Os₉CO ₂₄

] (

a maximum value for u of 22.58. Three standard reflec-

tions were monitored after every 100 reflections col-

lected and showed a decrease in standard intensity

during the data collection time of y35%; a linear decay

correction was applied to compensate for this apparent

decay of X-ray intensity. A total of 12 021 reflections

were measured within the range 0FhF18, y18Fk

F16, y16FlF16 and averaged to yield 9975 unique

{

(

)

}

)

Au PCy₃

Os₉Au₂P₂O₂₄C₆₀H₆₆, triclinic, space group P1, a

Ž .

93.55 5 , b s 105.06 4 , g s 116.19 4 8, U s

s 17.002 8 , b s 17.134 8 , c s 15.385 6 A, a s

Ž . Ž . Ž .

Ž .

3802 3 A , Z s 2, F 000 s 2997, m Mo Ka s

18.939 mm^y1

D_cs2.932 g cm^y3. A brown block-

Ž .

reflections R_ints0.0577 of which 8952 were judged

shaped crystal of approximate dimensions 0.24=0.28

=0.30 mm³was mounted on a glass fibre, D_mnot

recorded, accurate lattice parameters determined from

as significant by the criterion that F_obs)4s F_obs

Corrections for Lorentz and polarisation effects were

applied. Absorption corrections was applied using

semi-empirical c scans, minimum and maximum trans-

mission coefficients 0.3517 and 1.0000 respectively.

25 reflections us17.30–18.028 . Intensity data were

measured on a Rigaku AFC7R diffractometer using

monochromated Mo Ka radiation and v scan mode to

Table 3

Atomic coordinates and equivalent isotropic displacement parameters A for 1b

Ž .

Au 1

Au 2

Ž .

0.22244 4

0.27151 5

Ž .

0.14958 8

0.21578 9

Ž .

0.0548 4

0.0657 5

Ž .

0.088 2

0.084 2

Ž .

0.265 3

0.179 3

0.1652

C 42

0.1559 11

0.055 10

0.089 14

Ž .

0.0217 2

Ž .

C 43

0.0674 14

Ž .

0.080 12

Os 1

0.19522 4

0.04031 7

0.0345 2

0.0447 4

C 51

0.2561 13

0.030 2

y0.198 3

Ž .

0.074 12

Os 2

0.15021 4

0.08535 8

y0.12586 14

0.0026 2

0.0473 4

C 52

0.2669 12

0.183 2

y0.175 3

Ž .

y0.060 3

0.078 12

Os 3

0.18122 4

0.19011 7

0.0461 4

C 53

0.2962 13

0.078 2

Ž .

0.065 11

Os 4

Ž .

0.12654 4

0.11019 7

Ž .

0.1474 2

0.0492 4

C 61

0.1780 12

y0.080 2

0.260 3

Ž .

0.062 10

Os 5

0.24251 4

0.10275 8

y0.10888 14

0.0512 4

C 62

0.1671 11

y0.160 2

0.107 3

Ž .

Os 6

0.14581 5

y0.06112 8

0.1462 2

0.0558 4

C 63

0.090 2

y0.106 3

0.191 3

0.10 2

Ž .

0.054 9

Ž .

y0.123 2

Os 7

0.06105 4

Ž .

0.04968 9

y0.1467 2

0.0585 4

Ž .

C 71

y0.0013 11

0.046 2

Ž .

y0.203 3

Os 8

Ž .

0.08761 4

0.17293 8

Ž .

y0.0198 2

0.0532 4

C 72

0.0570 11

y0.043 2

0.066 10

Ž .

0.067 11

Os 9

0.10474 4

0.00926 7

0.0085 2

Ž .

0.0479 4

C 73

0.0528 12

0.103 2

y0.257 3

Ž .

0.031 3

0.099 14

P 1

0.2661 3

0.1973 5

0.2811 7

0.057 3

C 81

0.0862 14

0.270 3

Ž .

O 11

Ž .

0.085 13

P 2

0.3369 3

Ž .

0.2707 5

0.0722 7

0.058 3

Ž .

C 82

0.0687 13

0.225 2

Ž .

y0.124 3

Ž .

0.024 3

0.075 11

0.2157 7

y0.1018 13

y0.080 2

0.061 6

C 83

0.0287 13

0.154 2

Ž .

0.072 11

O 12

0.2645 8

y0.0404 14

0.155 2

Ž .

0.077 7

C 91

0.0449 12

y0.019 2

0.032 3

Ž .

0.058 10

O 21

0.1600 9

0.186 2

y0.293 2

0.098 9

C 92

0.1116 11

y0.091 2

y0.041 3

Ž .

0.064 10

O 22

0.1584 7

Ž .

y0.0585 14

y0.240 2

0.064 7

Ž .

C 01

0.3453 11

0.251 2

Ž .

0.187 2

Ž .

0.346 2

Ž .

0.071 11

O 31

0.1845 8

0.109 2

0.076 7

C 02

0.3048 12

0.273 2

0.240 3

Ž .

0.071 11

O 32

0.1835 9

0.305 2

y0.152 2

0.094 9

C 111

0.2284 12

0.248 2

0.360 3

Ž .

0.078 12

O 41

0.1081 9

0.274 2

0.221 2

0.095 9

C 112

0.2035 12

0.305 2

0.340 3

Ž .

0.099 14

O 42

0.1627 9

0.078 2

0.336 2

Ž .

0.092 9

C 113

0.173 2

0.349 3

Ž .

0.390 3

Ž .

0.2592 11

Ž .

0.114 11

Ž .

O 43

0.0347 9

0.061 2

0.216 2

0.089 8

C 114

0.177 2

Ž .

0.320 3

0.480 4

0.13 2

Ž .

0.517 4

Ž .

O 51

y0.013 2

y0.262 2

C 115

0.203 2

0.269 3

0.13 2

Ž .

0.231 2

Ž .

0.452 3

O 52

0.2813 11

y0.227 2

0.116 11

C 116

0.2322 13

0.228 2

0.082 13

Ž .

0.068 11

O 53

0.3322 10

0.051 2

y0.029 2

0.103 9

C 121

0.2978 12

0.127 2

0.343 3

Ž .

0.084 12

O 61

0.1971 11

y0.090 2

0.322 2

0.112 11

C 122

0.2850 13

0.048 2

0.347 3

Ž .

O 62

0.1750 9

y0.222 2

0.085 2

Ž .

0.098 9

C 123

0.303 2

y0.007 3

0.401 3

0.11 2

Ž .

y0.128 2

Ž .

0.013 4

Ž .

O 63

0.0580 10

0.218 2

0.099 9

C 124

0.339 2

0.447 4

0.14 2

Ž .

O 71

y0.0402 10

0.041 2

y0.115 2

0.103 9

C 125

0.357 3

Ž .

0.088 5

0.432 6

0.22 4

Ž .

O 72

0.0586 10

y0.104 2

y0.243 2

0.106 10

C 126

0.337 2

0.147 3

0.388 3

0.10 2

Ž .

O 73

0.0498 10

0.135 2

y0.324 2

0.113 11

C 211

0.3397 11

0.374 2

0.061 3

0.063 10

Ž .

0.051 2

Ž .

0.064 10

O 81

0.0842 10

0.340 2

0.107 10

C 212

0.3001 12

0.420 2

0.054 2

Ž .

0.083 12

O 82

0.0673 9

0.265 2

y0.190 2

0.093 9

C 213

0.3031 13

0.505 2

0.046 3

Ž .

0.093 13

O 83

y0.0073 9

0.150 2

0.049 2

0.092 9

Ž .

C 214

0.3451 13

0.541 3

0.041 3

Ž .

0.069 11

O 91

0.0085 9

y0.037 2

0.055 2

0.085 8

C 215

0.3837 12

0.497 2

0.053 3

Ž .

0.063 10

O 92

0.1175 8

y0.1522 14

y0.071 2

0.071 7

C 216

0.3817 11

0.413 2

0.062 2

Ž .

y0.041 2

Ž .

y0.039 2

Ž .

C 11

0.2109 10

0.048 8

Ž .

C 221

0.3877 9

0.231 2

0.025 2

0.043 8

Ž .

0.13 2

Ž .

y0.073 4

C 12

0.2366 10

y0.011 2

0.116 2

0.049 9

C 222

0.389 2

Ž .

0.253 3

Ž .

C 21

0.1533 13

0.147 2

y0.235 3

0.080 12

C 223

0.433 2

0.222 3

y0.108 4

0.14 2

Ž .

y0.191 3

Ž .

y0.075 4

Ž .

C 22

0.1600 11

y0.001 2

0.061 10

C 224

0.464 2

0.176 3

0.14 2

Ž .

0.071 3

Ž .

C 31

0.1840 11

0.280 2

0.063 10

C 225

0.457 2

0.159 3

0.006 4

0.11 2

Ž .

C 32

0.1841 14

0.261 3

y0.097 3

0.089 13

C 226

0.4165 14

0.189 3

0.062 3

0.10 2

Ž .

C 41

0.1181 13

0.217 2

0.194 3

0.079 12

is defined as one-third of the trace of the orthogonalised U tensor.

i j

(

)

138

Z. Akhter et al.rJournal of Organometallic Chemistry 550 1998 131–139

Structure solution was by a combination of direct meth-

ods and Fourier techniques. During the refinement pro-

cess it became apparent that there was approximately

tively small proportion of disorder, no alternative sites

for the carbonyl ligands were located or assigned. In

addition, the chlorine atoms of a molecule of CH₂Cl₂

with 20% occupancy were located and included in

subsequent refinement. Anisotropic thermal motion was

assumed for the osmium, gold and phosphorus atoms.

Hydrogen atoms were placed in calculated positions and

Ž .

20% disorder of Os 1 , with its alternative position

Ž .

capping the face consisting of atoms Os 4 , Os 6 ,

Ž .

Os 8 . Alternative positions were also located and as-

signed to Os 2 and Os 8 ; however, due to the rela-

Ž .

Table 4

Atomic coordinates and equivalent isotropic displacement parameters A for 2b

Ž .

Os 3

Os 4

Ž .

0.0496 2

Ž .

0.233 2

0.124 2

Ž .

y0.797 2

Ž .

0.067 6

y0.21398 6

y0.35554 5

y0.80547 6

0.0463 2

C 42

y0.173 2

Ž .

0.12747 6

Ž .

y0.21252 6

Ž .

y0.76334 6

Ž .

y0.322 2

Ž .

y0.749 2

Ž .

0.061 6

C 43

Ž .

y0.679 2

Ž .

0.053 5

Os 5

y0.02735 5

y0.25738 5

y0.70018 5

0.0412 2

C 51

y0.028 2

y0.3627 14

Ž .

0.04829 6

Ž .

y0.14620 6

Ž .

y0.90839 6

Ž .

y0.577 2

Ž .

0.050 5

Os 6

0.0474 2

C 52

0.043 2

y0.2168 14

Ž .

y0.942 2

Ž .

0.064 6

Os 7

y0.10683 5

y0.19070 5

y0.84550 5

0.0394 2

C 61

0.157 2

y0.102 2

Ž .

y0.11992 6

Ž .

y0.16426 5

Ž .

y0.67097 5

Ž .

y1.032 2

Ž .

0.058 6

Os 9

0.0406 2

C 62

y0.027 2

y0.188 2

Ž .

0.062 2

Ž .

y0.912 2

Ž .

0.060 6

Au 1

y0.28002 5

y0.22179 5

y0.83405 6

0.0463 2

C 63

y0.031 2

Ž .

y0.14611 6

Ž .

y0.32780 5

Ž .

y0.59783 6

Ž .

0.046 5

Au 2

0.0484 2

C 71

y0.1820 14

y0.2317 13

y0.9672 14

Ž .

0.054 5

P 1

y0.4110 4

y0.2054 4

y0.8793 4

0.0500 13

C 72

y0.114 2

y0.087 2

y0.867 2

Ž .

y0.1816 4

Ž .

y0.3939 4

Ž .

y0.4773 4

Ž .

0.063 6

P 2

0.0531 14

C 81

0.126 2

Ž .

y0.036 2

y0.594 2

Ž .

Os 1

0.07254 8

y0.29992 7

y0.95560 8

0.0511 3

C 82

0.194 2

y0.007 2

y0.734 2

0.056 11

Ž .

y0.3207 2

Ž .

y0.8809 2

Ž .

Os 2

y0.0606 2

0.0382 5

C 83

0.0589 14

0.0221 14

y0.7218 14

0.049 5

Ž .

Os 8

0.0806 2

y0.0758 2

y0.7217 3

0.0422 6

Ž .

C 91

y0.1295 13

y0.0572 13

y0.6891 13

0.043 5

Ž .

y0.0158 4

Ž .

y0.7382 5

Ž .

0.045 5

Os 1B

0.2201 4

0.057 2

C 92

y0.0539 14

y0.1207 13

y0.5465 14

Ž .

0.065 6

Os 2B

0.0532 9

y0.0929 10

y0.7125 12

0.045 3

C 93

y0.224 2

y0.203 2

y0.636 2

Ž .

0.086 10

Ž .

Os 8B y0.0335 7

y0.3191 10

y0.8881 10

0.038 2

C 111 y0.454 2

y0.222 2

y1.008 2

0.066 6

Ž .

Cl 1 y0.549 3

y0.116 3

y0.599 3

C 121 y0.510 2

y0.287 2

y0.850 2

0.083 8

Ž .

Cl 2

y0.390 4

y0.124 4

y0.501 4

0.13 2

C 131 y0.387 2

y0.092 2

y0.840 2

0.063 6

Ž .

0.241 2

Ž .

O 11

y0.225 2

y1.015 2

0.144 10

C 211 y0.255 2

y0.361 2

y0.432 2

0.079 7

Ž .

O 12

y0.054 2

y0.391 2

y1.150 2

0.108 7

C 221 y0.240 2

y0.516 2

y0.506 2

0.082 8

Ž .

0.096 2

Ž .

0.055 5

O 13

y0.464 2

y0.935 2

0.107 7

C 231 y0.076 2

y0.3591 14

y0.380 2

Ž .

0.121 12

O 21

y0.1994 13

y0.4074 12

y1.0694 13

0.081 5

Ž .

C 112 y0.480 3

y0.313 2

y1.056 3

Ž .

0.15 2

O 22

y0.0737 11

y0.5013 11

y0.8667 11

0.068 4

C 113 y0.509 3

y0.325 3

y1.158 3

Ž .

0.16 2

O 31

y0.2335 14

y0.5386 14

y0.8017 14

0.094 6

C 114 y0.449 3

y0.251 3

y1.188 3

Ž .

O 32

y0.3581 13

y0.4380 12

y0.9899 13

0.084 5

C 115 y0.420 3

y0.159 3

y1.147 3

0.125 13

Ž .

O 33

y0.3761 14

y0.4176 13

y0.7314 14

0.090 6

Ž .

C 116 y0.382 2

y0.155 2

y1.042 2

0.096 9

Ž .

O 41

0.2514 13

y0.1356 12

y0.5662 13

0.081 5

C 122 y0.601 2

y0.283 2

y0.889 3

0.106 10

Ž .

O 42

0.309 2

y0.135 2

y0.808 2

0.111 7

C 123 y0.685 3

y0.366 3

y0.876 3

0.16 2

Ž .

O 43

0.1337 12

y0.0224 12

0.0922 12

y0.3838 12

y0.7372 12

0.077 5

C 124 y0.666 3

y0.379 3

y0.787 3

0.112 11

Ž .

0.112 11

O 51

y0.4260 11

y0.6615 12

0.075 5

Ž .

C 125 y0.583 2

y0.384 2

y0.751 3

Ž .

0.125 13

O 52

y0.1923 11

y0.4990 12

0.070 4

C 126 y0.496 3

y0.298 3

y0.761 3

Ž .

O 61

0.220 2

y0.0684 14

y0.966 2

0.100 6

C 132 y0.361 2

y0.065 2

y0.735 2

0.067 6

Ž .

O 62

y0.0677 12

y0.2119 11

y1.1085 12

0.069 4

C 133 y0.322 2

0.034 2

y0.705 2

0.092 9

Ž .

O 63

0.0752 11

0.0405 11

y0.9161 11

0.069 4

Ž .

C 134 y0.383 3

0.068 3

Ž .

y0.753 3

0.123 12

Ž .

O 71

y0.2308 12

y0.2538 11

y1.0412 12

0.069 4

C 135 y0.410 3

0.043 2

y0.850 2

0.115 11

Ž .

O 72

y0.1196 11

y0.0264 10

y0.8890 11

0.065 4

C 136 y0.454 2

y0.059 2

y0.886 2

0.093 9

Ž .

O 81

0.1619 12

y0.0009 11

y0.5169 12

0.073 5

C 212 y0.256 2

y0.383 2

y0.337 2

0.101 10

Ž .

y0.347 3

Ž .

y0.307 3

Ž .

O 82

0.266 2

0.034 2

y0.739 2

0.110 8

C 213 y0.318 3

0.16 2

Ž .

0.062 4

Ž .

O 83

0.0539 11

0.0862 10

0.0043 10

y0.7260 11

C 214 y0.417 3

y0.386 3

y0.371 3

0.137 14

Ž .

O 91

y0.1324 10

y0.6952 10

0.058 4

C 215 y0.406 3

y0.357 3

y0.461 3

0.131 13

Ž .

O 92

y0.0175 11

y0.0891 10

y0.4705 11

0.063 4

C 216 y0.351 2

y0.394 2

y0.498 2

0.080 8

Ž .

O 93

y0.2877 13

y0.2214 12

y0.6047 13

0.083 5

Ž .

C 222 y0.244 3

y0.567 2

y0.432 2

0.110 11

Ž .

y0.665 3

Ž .

y0.470 3

Ž .

C 11

0.171 2

y0.253 2

y0.995 2

0.092 9

C 223 y0.290 3

0.15 2

Ž .

C 12

0.001 3

Ž .

y0.353 3

y1.076 3

0.124 12

C 224 y0.290 3

y0.700 3

y0.549 3

0.138 14

Ž .

0.113 11

C 13

0.082 2

y0.398 2

y0.944 2

0.089 9

C 225 y0.303 3

y0.655 2

y0.623 3

Ž .

y0.553 3

Ž .

y0.579 3

Ž .

C 21

y0.141 2

y0.3735 14

y0.996 2

0.054 5

Ž .

C 226 y0.232 3

0.16 2

Ž .

y0.404 2

Ž .

C 22

y0.069 2

y0.433 2

y0.872 2

0.054 5

C 232 y0.013 2

y0.392 2

0.064 6

Ž .

0.076 2

Ž .

C 31

y0.221 2

y0.466 2

y0.800 2

0.079 8

C 233

y0.361 2

y0.322 2

0.099 10

Ž .

0.104 10

C 32

y0.301 2

y0.400 2

y0.922 2

0.060 6

C 234

0.123 2

y0.263 2

y0.289 2

Ž .

C 33

y0.312 2

Ž .

y0.391 2

Ž .

y0.756 2

Ž .

0.064 6

Ž .

C 235

0.066 2

y0.229 2

Ž .

y0.262 2

Ž .

0.079 7

Ž .

C 41

0.202 2

y0.164 2

y0.643 2

0.070 7

C 236 y0.025 2

y0.261 2

y0.343 2

0.070 7

is defined as one-third of the trace of the orthogonalised U tensor.

i j

(

)

Z. Akhter et al.rJournal of Organometallic Chemistry 550 1998 131–139

139

refined using a riding model, with the thermal parame-

Crystallographic Data Centre for assistance with the

purchase of the X-ray equipment.

ters being held constant at 0.08 A . Full matrix least

squares refinement on F_o²_bsfor 9974 data and 489

parameters converged to wR2s0.1402 all data , con-

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program packages 14–16 . Atomic coordinates and

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Ž .

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Ž .

4. Conclusion

Ž .

The results of the above study show that the cluster

Commun. 1982 773.

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found that the latter product has undergone a major

rearrangement of the metal core geometry. In contrast

reaction with the digold reagent ‘‘Au₂L^2q’’ results in

the formation of a cluster where the osmium framework

retains its original geometry, albeit with the loss of a

carbonyl ligand. The isolation and characterisation of

these products clearly demonstrate the flexibility that

appears to be an inherent property of high nuclearity

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arises from a subtle balance between the electronic

properties of the metal core and the steric requirements

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Acknowledgements

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14 TEXSAN: Single Crystal Structure Analysis Software, Version

We gratefully acknowledge the E.P.S.R.C. S.L.I. ,

the Cambridge Commonwealth Trust and the UK Com-

1.6, 1993, Molecular Structure Corporation, The Woodlands,

TX 77381, USA.

mittee of Vice Chancellors and Principals Z.A. for

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osmium salts, and the E.P.S.R.C. and The Cambridge

15 G.M. Sheldrick, Acta Crystallogr. Sect. A: 46 1993 467.

16 G.M. Sheldrick, SHELXL-93, Program for Structure Refinement,

University of Gottingen, 1993.

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