Proton-Coupled Electron Transfer at the Surface of Polyoxovanadate-Alkoxide Clusters

[Image: see text] Proton-coupled electron transfer (PCET) is a fundamental process involved in all areas of chemistry, with relevance to biological transformations, catalysis, and emergent energy storage and conversion technologies. Early observations of PCET were reported by Meyer and co-workers in 1981 while investigating the proton dependence of reduction of a molecular ruthenium oxo complex. Since that time, this conceptual framework has grown to encompass an enormous scope of charge transfer and compensation reactions. In this Account, we will discuss ongoing efforts in the Matson Laboratory to understand the fundamental thermodynamics and kinetics of PCET processes at the surface of a series of Lindqvist-type polyoxovanadate clusters. This project aims to provide atomistic resolution of net H atom uptake and transfer at the surfaces of transition-metal oxide materials. First, we discuss our efforts aimed at understanding PCET at metal oxide surfaces using the Lindqvist-type polyoxovanadate-alkoxide (POV-alkoxide) cluster [(n)Bu(4)N](2)[V(6)O(13)(TRIOL(NO(2)))(2)]. These clusters reversibly bind H atom equivalents at bridging oxide sites, mirroring the proposed uptake and release of e(–)/H(+) pairs at transition-metal oxide surfaces. Summarized results include the measurement of bond dissociation free energies of surface hydroxide moieties (BDFE(O–H)) as well as mechanistic analyses that verify concerted proton electron transfer as the operative pathway for PCET at the surface of POV-alkoxide clusters. Next, we discuss net proton and H atom uptake at the surface of reduced variants of the Lindqvist-type POV-alkoxide cluster, [V(6)O(7)(OR)(12)](n) (R = Me, Et; n = −2, −1, 0, + 1). In the case of these low-valent POV-alkoxide clusters, nucleophilic bridging sites are kinetically inhibited by functionalization of the cluster surface with organic ligands. This molecular modification enables site-selectivity in proton and H atom uptake to terminal oxide sites. The impact of reaction site and cluster electronics on reaction driving force of PCET is explored, with core electron density playing a critical role in dictating thermodynamics of H atom uptake and transfer. Additional work described here contrasts the kinetics of PCET at terminal oxide sites to the reactivity observed at bridging oxides in POV-alkoxide clusters. Overall, this Account summarizes our foundational knowledge regarding the assessment of PCET reactivity at the surfaces of molecular metal oxides. Drawing analogies between POV-alkoxide clusters and nanoscopic metal oxide materials provide design principles for the advancement of materials applications with atomic precision. These complexes are additionally highlighted as tunable redox mediators in their own right; our studies demonstrate how cluster surface reactivities can be optimized by modifying electronic structure and surface functionalities.