Chemically Reversible Four-Electron Oxidation and Reduction Utilizing Two Inorganic Functional Groups

Abstract

Four-electron oxidation of the quadruply bonded W(2)(II,II) compound W(2)(2,2'-dipyridylamide)(4), 1, results in the formation of a novel, diamagnetic ditungsten terminal oxo compound [W(2)O(2,2'-dipyridylamide)(4)](2+), 2. In contrast to the chemical inertness of mononuclear tungsten oxo species, 2 undergoes a four-electron reduction including oxygen-atom transfer in reactions with excess tri-tert-butylphosphine in acetonitrile to recover 1. This unusual chemically reversible multielectron reactivity is ascribed to the cooperation of W-O and W-W multiple bonding.