Mononuclear hydrido alkyl carbonyl complexes of osmium and their polynuclear derivatives

Article abstract of DOI:10.1021/ic00141a019

Osmium hydrido alkyl carbonyl complexes cis-Os(CO)₄(H)R (R = Me, Et) can be prepared by alkylation of [Os(CO)₄H]^- with the corresponding alkyl fluorosulfates. The thermal decomposition of these complexes gives dinuclear and trinuclear derivatives HOs₂(CO)₈R and ROs₃(CO)₁₂R. Other dinuclear complexes can be obtained from similar reactions of hydrides with alkyl carbonyl complexes. The course of the reaction of cis-Os(CO)₄(H)CH₃ with Ph₃P depends upon the reaction conditions: with complete exclusion of air (Ph₃P)Os(CO)₄ and CH₄ are obtained, whereas small amounts of air induce the rapid operation of a radical-chain substitution mechanism and the formation of Os(CO)₃(PPh₃)(H)CH₃.