Germanium clusters complexes

3 Germanium clusters/com-plexes 24.3.1 Germanium clusters/complexes Table 24.3.1 BDEs in Germanium Clusters/Complexes  

The broken bonds (boldface = dissociated fragment) BDEs (boldface= recommended data Methods (reference in  

2 Germanium-ion clusters/complexes Table 24.3.2 BDEs in Germanium-Ion Clusters/Complexes  

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A few clusters of interest containing germanium and transition metals have been reported.136-138 Dimethylgermane was found to replace only the bridging carbonyls between cobalt in a mixed germanium/cobalt/iron cluster complex (Equation (107)), and replacement of the carbonyl bridging the iron metal centers was not observed.137 A similar reaction leads to replacement of a bridging carbonyl in a mixed cobalt/silicon cluster (Equation (108)).136... 

Very few examples of these species have appeared since the field was last reviewed.1 One species of interest is the seven-membered heterocycle 100, which was obtained from the dilithiated species 97 via the formation of a Ge=B doubly bonded intermediate (Scheme 30).206 A rare example of a germanium/gallium cluster complex has also been prepared (Equation (162)).207... 

There are a sufficiently large number of complexes, mainly of germanium, containing more than one type of transition metal, to warrant a separate discussion some examples have already been mentioned (viz. 38 and 57). Mackay and Nicholson (89,91) have described the reaction between [Fe2-(CO)8(//-GeH2)2] and [Co2(CO)8], which affords the mixed cobalt-iron clusters [Fe2(CO)8 /i-Ge(Co2(CO)7) 2], 82, and [Fe2(CO)7 /i-Ge(Co2-(CO)7) 2], 83, the latter having been characterized by X-ray diffraction. This is isoelectronic with the iron-germanium cluster, 63, and both adopt very similar structures. 

The single-bond compounds between Si, Ge, and Sn and chalcogens (S, Se, Te) are reactive and used as synthetic intermediates in the synthesis of organic compounds, organochalcogen compounds, organo-silicon, -germanium and -tin compounds, and transition metal-chalcogen complexes and clusters. 

Germanes hydride, 2 76 reactivity of, 2 87 Germanium anionic cluster, 24 227 azides, preparation, 9 138 properties, 9 135-136, 139, 141 binary carbide not reported, 11 211 carbides, preparation of, 11 163 chalcogenide halides, 23 390 chlorides, mass spectra of, 18 248, 249 complexes, xenon fluoride reactions, 46 85 compounds, see also Organogermanium compounds... 

Fe—Fe bond present in 58 is bridged by two carbonyls, contrasting with the absence of bridging carbonyls in 56. The tin analogue of 58, [Sn Fe2(CO)8 - Fe(CO)4 2]2, 59, has also been synthesized by a similar route (71), and oxidation by Cu(l) proceeds in a similar manner to the example for lead and provides another synthetic route to 54. With germanium, however, the more condensed cluster species [Ge Fe3(CO)10 Fe(CO)4 ]2 , 60, is formed (77), although oxidation of this complex with Cu(I) affords 55, analogous to the formation of 54 and 56 from 59 and 58, respectively. 

Finally, we note a number of higher nuclearity iron-containing clusters. Hieber (74) reported a complex formulated as [Sn2Fe5(CO)2o], 62, although no structural details were presented. Hieber also described a complex formulated as [PbFe3(CO)12], but later work by Whitmire (71) indicates that this compound is probably the tetrairon species, 56. Mackay and Nicholson (75) have described the synthesis and structures of three polynuclear species [Fe2(CO)7 //-E(Fe2(CO)8) 2] (63, E = Ge 64, E = Sn) and [Fe3(CO)10- //-Ge(Fe2(CO)8) 2], 65, from reactions involving germanium or tin... 

Examples of nickel complexes are rare and are confined to three reported nickel carbonyl clusters containing interstitial germanium or tin atoms (90). The reaction between [Ni6(CO)l2]2 and GeCl4 affords two species, [Ni10Ge(CO)2o]2 , 79, and [Ni12Ge(CO)22]2, 80. The former structure is based on a pentagonal antiprismatic framework of nickel atoms with an... 

In the report that described the synthesis of 108 (777), Whitmire also observed that the reaction between NaBi03 and methanolic [Fe(CO)s] in the presence of hydroxide afforded the trianionic species [Bi Fe(CO)4 4]3, 110, which was subsequently characterized by X-ray crystallography (775). Cluster 110 contains a central bismuth atom tetrahedrally coordinated by four Fe(CO)4 fragments and is isoelectronic with the anionic tetracobalt-indium complex, 27, and the neutral tetracobalt-germanium, - tin, and -lead complexes, 68, 71, and 72. Oxidation of 110 affords 108 (777), while acidification (772) yields the hydride-containing cluster [BiFe3(CO)9(/i-H)3], 111, which also contains a tetrahedral BiFe3 core. Johnson and Lewis (114) have... 

Polysulfanides, in Ru and Os half-sandwich complexes, 5-Gp and 7 5-indenyl compounds, 6, 496 Polysulfide rings, with germanium, 3, 742-743 Polysulfides, in Ru and Os half-sandwich complexes, rjS-Cp and ]5-indenyl compounds, 6, 496 Polysulfido nitrosyl complexes, with chromium, 5, 303 Polytetrafluoroethylene valves, in high vacuum lines, 1, 198 Polythiaether macrocyclic ligands, in hexaruthenium carbido clusters, 6, 1018-1019... 

A further extension of the known isoelectronic series in the class of icosahedral species has been reported by Todd and Beer (212). Substitution of a C—H fragment in the complexes LXIV and LXV by a bare phosphorus or arsenic atom leads to the closo-cluster compounds LXVI and LXVII, which are here also described as n complexes with regard to their synthesis. Treatment of the disodium salt of the 7,8-ElCHB9H dianion (El = P, As) with a germanium(II) species results in the formation of the... 

Halide complexes of Group 14 metals continue to offer surprises in their structural chemistry. A new fluoro complex of germanium GeyFig has been isolated from the decomposition of germanium(IV) fluoride and shown by crystallography to comprise sheets of [GegFio] clusters... 

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