Oxidation-addition reactions of some isonitrile complexes of rhodium(I)

Abstract

Oxidative-addition of bromine or iodine to the complexes [(RNC)₄Rh]⁺, trans-[(RNC)₂(R′₃P)₂Rh]⁺, and trans-(RNC)₂Rh(CO)X (R =p-Me·C₆H₄, p-MeO·C₆H₄, p-ClC₆H₄; R′₃= Ph₃, Ph₂Me; X = Cl, Br) occurs by trans-addition. None of the complexes reacts with hydrogen chloride or bromide. The complexes (MeOC₆H₄NC)₂Rh-(CO)X₃ are unstable to loss of carbon monoxide in solution. The complex (MeOC₆H₄NC)₂Rh(CO) Cl reacts with methyl iodide to form the five-co-ordinate acetyl complex (MeOC₆H₄NC)₂Rh(COMe)I₂.