Ligand-Enabled Disproportionation of 1,2-Diphenylhydrazine at a PV-Center**

Abstract

We present herein the synthesis of a nearly square-pyramidal chlorophosphorane supported by the tetradentate bis(amidophenolate) ligand, N,N′-bis(3,5-di-tert-butyl-2-phenoxy)-1,2-phenylenediamide. After chloride abstraction the resulting phosphonium cation efficiently promotes the disproportionation of 1,2-diphenylhydrazine to aniline and azobenzene. Mechanistic studies, spectroscopic analyses and theoretical calculations suggest that this unprecedented reactivity mode for PV-centres is induced by the high electrophilicity at the cationic PV-center, which originates from the geometry constraints imposed by the rigid pincer ligand, combined with the ability of the o-amidophenolate moieties to act as electron reservoir. This study illustrates the promising role of cooperativity between redox-active ligands and phosphorus for the design of organocatalysts able to promote redox processes.