Alkyl compounds of ruthenium-(III) and -(V) and osmium(III). X-Ray crystal structures of hexakis(trimethylsilylmethyl)- and hexakis(neopentyl)diruthenium(III), dioxohexakis(trimethylsilylmethyl)diruthenium(V), and bis(η3-allyl)tetrakis(neopentyl)diosmium(III)

Abstract

The interaction of MgRCl or MgR₂, R = CH₂SiMe₃ or CH₂CMe₃, with Ru₂(µ-O₂CMe)₄Cl or Os₂(µO₂CMe)₄Cl₂ leads to the compounds M₂R₆ and M₂R₄(µ-O₂CMe)₂; diruthenium(II) tetra-acetate, Ru₂(µ-O₂CMe)₄, is formed in some of these alkylations. Interaction of Ru₂R₄(µ-O₂CMe)₂ with MgMe₂ or MgEt₂ gives the corresponding mixed hexa-alkyls. Interaction of Ru₂R₆ with oxygen gives the unique ruthenium(V) oxoalkyls R₃Ru(O)Ru(O)R₃, while interaction of Os₂(µ-O₂CMe)₂(CH₂CMe₃)₄ with allylmagnesium halide gives Os(η³-C₃H₅)₂(CH₂CMe₃)₄. X-Ray crystal structures of the two diruthenium hexa-alkyls, the ruthenium oxoalkyl, and the diosmium tetra-alkylbis(allyl) have been determined. The ruthenium(V) oxo trimethylsilylmethyl has been shown to react stoicheiometrically with propene to give the epoxide. It also reacts with PhNCO and Me₃SiNPMe₃ to give the respective ruthenium(V) imido complexes, Ru₂(NR)₂(CH₂SiMe₃)₆.