Vanadium Pyridonate Catalysts: Isolation of Intermediates in the Reductive Coupling of Alcohols

The reductive coupling of alcohols using vanadium pyridonate catalysts is reported. This attractive approach for C­(sp³)–C­(sp³) bond formation uses an oxophilic, earth-abundant metal for a catalytic deoxygenation reaction. Several pyridonate complexes of vanadium were synthesized, giving insight into the coordination chemistry of this understudied class of compounds. Isolated intermediates provide experimental mechanistic evidence that complements reported computational mechanistic proposals for the reductive coupling of alcohols. In contrast to previous mononuclear vanadium­(V)/vanadium­(III)/vanadium­(IV) cycles, this pyridonate catalyst system is proposed to proceed by a vanadium­(III)/vanadium­(IV) cycle involving bimetallic intermediates.