Syntheses and redox properties of the first phosphirene–dinitrogen and phosphirene–diazenide complexes

Abstract

The first mixed phosphirene–dinitrogen and phosphirene–diazenide complexes mer-[ReCl(N₂)(PPhCPhCPh)L₃] (L = PMe₂Ph 1a or PMePh₂ 1b) and [ReBr(NNPh)₂(PPhCPhCPh)₂(PPh₃)] 2 have been prepared by treatment of the corresponding thf solutions of trans-[ReCl(N₂)L₄] or [ReBr₃(NNPh)(PPh₃)₂] with PPhCPhCPh. Their redox properties have been investigated by cyclic voltammetry in an aprotic medium, at a platinum electrode, and the electrochemical E_L and P_L parameters estimated for the phosphirene ligand indicating that its overall electron donor/acceptor properties are similar to those of PMePh₂.