Cobalt carbonyl hydride structures

In solution these carbonyl hydrides act as very weak monobasic acids. The iron and cobalt carbonyl hydrides arc isoelectronic with Ni(CO)4 and have the same tetrahedral structure ... 

Huo et al. studied the structure and energies of cobalt-carbonyl radicals as well as the cationic and anionic homoleptic mononuclear cobalt-carbonlys and the cobalt-carbonyl hydrides.35 The B3LYP functional was applied with all-electron triple- quality basis. They found that most of these complexes prefer less symmetrical structures and minor structural deformations may result in large energetic differences. 

Nishinaga and co-workers isolated a series of stable cobalt(III)-alkyl peroxide complexes such as (170) and (171) in high yields from the reaction of the pentacoordinated Co"-Schiff base complex with the corresponding phenol and 02 in CH2C12. Complex (170 R=Bu ) has been characterized by an X-ray structure. These alkyl peroxide complexes presumably result from the homolytic addition of the superoxo complex Co111—02 to the phenoxide radical obtained by hydrogen abstraction from the phenolic substrate by the CoUI-superoxo complex. The quinone product results from / -hydride elimination from the alkyl peroxide complex (172)561,56,565,566 The quinol (169) produced by equation (245) has been shown to result from the reduction of the CoIU-alkyl peroxide complex (170) by the solvent alcohol which is transformed into the corresponding carbonyl compound (equation 248).561... 

Unlike cobalt and rhodium, the chemistry of polynuclear iridium carbonyl derivatives has not been studied in detail (15a). Reduction of Ir4(CO)i2 under carbon monoxide with K2C03 in methanol gives the yellow tetranuclear hydride derivative [Ir4(CO)nH], whereas under nitrogen the brown dianion [Ir8(CO)2o]2- has been isolated as a tetraalkylam-monium salt (97). It has been suggested that the structure of the dianion could result from the linking of two iridium tetrahedra, although its formulation so far is based only on elemental analyses. Clearly such an interesting compound deserves further chemical and structural characterization. 

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