Insertion reactions of the [RhCl(PPh3)2] fragment into a phosphirene ring, and carbonylation of the resulting rhodium(III) complex. Crystal and molecular structures of [RhCl(PPhCPhCPh)(PPh3)2], [RhCl(PPhCPhCPhCO)(PPh3)2] and the novel dimeric complex [{RhCl(PPhCPhCPhCO)(PPh3)}2]

Abstract

The first example of insertion of the d⁸ Rh^I fragment [RhCl(PPh₃)₂] into a phosphirene ring system results in a five-coordinate Rh^III complex, which undergoes insertion of carbon monoxide to give either monomeric [[graphic omitted]O)(PPh₃)₂] or dimeric [{[graphic omitted]O)(PPH₃)}₂], the structures of which have been elucidated by NMR spectroscopy and single-crystal X-ray diffraction studies.