Chemistry of the metal carbonyls. Part LIX. Organo-silicon- and -tin-(carbonyl)osmium complexes

Abstract

Trimethyl-and triethyl-silane react with dodecacarbonyltriosmium at elevated temperatures or under u.v. irradiation in hexane to form the complexes R₃SiOs(CO)₄H, (R₃Si)₂Os(CO)₄, and [R₃SiOs(CO)₄]₂(R = Me or Et). These compounds are inter-related both thermally and upon further reaction with R₃SiH. From the reaction between Me₃SnH and Os₃(CO)₁₂ only Me₃SnOs(CO)₄H and (Me₃Sn)₂Os(CO)₄ are isolated. Treatment of [Me₃SiOs(CO)₄]₂ with sodium amalgam affords [Me₃SiOs(CO)₄]^–, from which the species Me₃SiOs(CO)₄X (X = H, Me, SnMe₃, or Ru(CO)₄SiMe₃) have been obtained. The n.m.r., i.r., and mass spectra of the new compounds are reported. A mechanism is proposed to account for the various products of the reactions between Group IVB hydrides R₃MH and the dodecacarbonyls of the iron triad.