Interaction of tris(triphenylphosphine)chlororhodium(I) with iodomethane, methylallyl, and allyl chloride

Abstract

The reaction of tris(triphenylphosphine)chlororhodium(I) with iodomethane is shown to give an octahedral complex of rhodium(III), [RhlCl(CH₃)(PPh₃)₂(ICH₃)], which contains not only a Rh–CH₃ group, but also unusually, a firmly co-ordinated iodomethane molecule. From the interaction of RhCl(PPh₃)₃ with allyl and 2-methylallyl chloride, the first simple allylic derivatives of rhodium are obtained. These compounds fall into three classes. The allylic group is σ-bonded in one class, π-bonded in the second, and σ+π-bonded in the third. The complexes are characterised, inter alia, by nuclear magnetic resonance spectroscopy.