Decoding Proton-Coupled Electron Transfer with Potential-p Ka Diagrams: Applications to Catalysis.

Abstract

The applied potential at which [NiII(P2PhN2Bn)2]2+ (P2PhN2Bn = 1,5-dibenzyl-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) catalyzes hydrogen production is reported to vary as a function of proton source p Ka in acetonitrile. By contrast, most molecular catalysts exhibit catalytic onsets at p Ka-independent potentials. Using experimentally determined thermochemical parameters associated with reduction and protonation, a coupled Pourbaix diagram is constructed for [NiII(P2PhN2Bn)2]2+. One layer describes proton-coupled electron transfer reactivity involving ligand-based protonation, and the second describes metal-based protonation. An overlay of this diagram with experimentally determined E cat/2 values spanning 15 p Ka units, along with complementary stopped-flow rapid mixing experiments to detect reaction intermediates, supports a mechanism in which the proton-coupled electron transfer processes underpinning the p Ka-dependent catalytic processes involve protonation of the ligand, not the metal center. For proton sources with p Ka values in the range 6-10.6, the initial species formed is the doubly reduced, doubly protonated species [Ni0(P2PhN2BnH)2]2+, despite a higher overpotential for this proton-coupled electron transfer reaction in comparison to forming the metal-protonated isomer. In this complex, each ligand is protonated in the exo position with the two amine moieties on each ligand binding a single proton and positioning it away from the metal center. This species undergoes very slow isomerization to form an endo-protonated hydride species [HNiII(P2PhN2Bn)(P2PhN2BnH)]2+ that can release hydrogen to close the catalytic cycle. Importantly, this slow isomerization does not perturb the initially established proton-coupled electron transfer equilibrium, placing catalysis under thermodynamic control. New details revealed about the reaction mechanism from the coupled Pourbaix diagram and the complementary stopped-flow studies lead to predictions as to how this p Ka-dependent activity might be engendered in other molecular catalysts for multi-electron, multi-proton transformations.