Selective Hydrogenation of Azobenzene to Hydrazobenzene via Proton-Coupled Electron Transfer from a Polyoxotungstate Cluster.

In this report, we describe proton-coupled electron transfer (PCET) reactivity at the surface of the Keggin-type polyoxotungstate cluster [BuN][PWO] () in acetonitrile. Bond dissociation free energies (BDFEs) of the O-H groups generated upon reduction of in the presence of acid are determined through the construction of a potential-p diagram. The surface O-H bonds are found to be weak (BDFE(O-H) < 48 kcal mol), comparable to the BDFE of H. This is consistent with the observed formation of H upon addition of a suitably strong organic acid, HNPh (p = 5.98), to the reduced form of the cluster. The one-electron reduced form of is isolated and used in conjunction with acid to realize the stoichiometric semihydrogenation of azobenzene via PCET from the surface of the reduced cluster.