Reactivity of Substituted Benzenethiols Towards Chlorotris(triphenylphosphine)iridium(I) and Chlorotris(triphenylarsine)iridium(I)

Abstract

A series of substituted benzenethiols, HSC6H4Y (Y = 4-Br, 4-F, 4-H, 4-CH3, or 4-CH3O) have been shown to react with IrCl(Ph3M′)3 (M′ = P or As) in benzene to form dimeric iridium(III) complexes of the type, [IrHCl(SC6H4Y)(Ph3M′)2]2, 1. The thiol, 4-nitrobenzenethiol, reacts with IrCl(Ph3M′)3(M′ = P or As) to form complexes of the type [IrCl2(SC6H4NO2)(Ph3M′)2]2, 2. Complexes 1 undergo reductive elimination with carbon monoxide to form trans-[Ir(CO)2(Ph3M′)2]Cl whereas complexes 2 do not react with carbon monoxide. Spectroscopic properties (i.r. and n.m.r.) of these complexes are discussed in relation to their structure in the solid state and in solution.