Substitution reactions on triosmium clusters of the type [Os3(µ-H)(µ-X)-(CO)10][X = NHMe, O2CR, C5H4N, or OC(NHMe); R = H, Me, or Ph]

Abstract

The reaction of [Os₃H(NHMe)(CO)₁₀] with Me₃NO in solvents containing acetonitrile produces three isomers of the acetonitrile derivative [Os₃H(NHMe)(CO)₉(MeCN)], (2a)–(2c), together with a trace of [Os₃H(NHMe)(CO)₉(NMe₃)]. The acetonitrile derivatives all react with P(OMe)₃ to give isomers of [Os₃H(NHMe)(CO)₉{P(OMe)₃}]. Prolonged reaction of (2c) with P(OMe)₃ results in two isomers of the disubstituted complex [Os₃H(NHMe)(CO)₈{(P(OMe)₃)}₂]. Reaction of Me₃NO with compounds of the type [Os₃H(µ-X)(CO)₁₀], where X is one of the bidentate ligands O₂CR (R = H, Me, or Ph), C₅H₄N, or O C(NHMe), results in the formation of the trimethylamine derivatives [Os₃H(X)(CO)₉(NMe₃)]. These compounds react with P(OMe)₃ to form [Os₃H(X)(CO)₉{P(OMe)₃}]. All the products were characterised by i.r., ¹H n.m.r., and mass spectroscopy and structural assignments made.