Engineering mechanisms of proton-coupled electron transfer to a titanium-substituted polyoxovanadate-alkoxide.

ABSTRACT: Metal oxides are promising catalysts for small molecule hydrogen chemistries, mediated by interfacial proton-coupled electron transfer (PCET) processes. Engineering the mechanism of PCET has been shown to control the selectivity of reduced products, providing an additional route for improving reductive catalysis with metal oxides. In this work, we present kinetic resolution of the rate determining proton-transfer step of PCET to a titanium-doped POV, TiV₅O₆(OCH₃)₁₃ with 9,10-dihydrophenazine by monitoring the loss of the cationic radical intermediate using stopped-flow analysis. For this reductant, a 5-fold enhanced rate (k _PT = 1.2 × 10⁴ M^-1 s^-1) is accredited to a halved activation barrier in c

SUBMITTER: Cooney SE 

PROVIDER: S-EPMC11733765 | biostudies-literature | 2025 Feb

REPOSITORIES: biostudies-literature