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

The first mixed phosphirene-dinitrogen and phosphirene-diazenide complexes mer-[ReCl(N-2)(PPhCPh=CPh)L-3] (L=PMe2Ph 1a or PMePh2 1b) and [ReBr(NNPh)(2 )(PPhCPh=CPh)(2)(PPh3)] 2 have been prepared by treatment of the correspond ing thf solutions of trans-[ReCl(N-2)L-4] or [ReBr3(NNPh)(PPh3)(2)] with PP hCPh=CPh. Their redox properties have been investigated by cyclic voltammet ry 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 PMeP h2.