Multisite Proton-Coupled Electron Transfer at a Keggin-Type Polyoxotungstate.

ABSTRACT: Proton-coupled electron transfer (PCET) governs many redox transformations, but is thermodynamically constrained when proton and electron transfer occur at a single site. Here, we introduce a new multisite PCET (MS-PCET) platform, based on the Keggin-type polyoxotungstate, [VW₁₂O₄₀]^3- (VW₁₂). Pairing VW₁₂ with either Brønsted bases or acids yields reagent pairs with tunable effective bond dissociation free energies (BDFE_eff) over 15 kcal mol^-1, enabling both oxidative and reductive H atom transfer reactions. Kinetic studies on the oxidative pathway by using 2,4,6-^tBu₃PhOH as a model hydrogen atom (H atom) donor reveal a product-like, entropy-dominated concerted pro

SUBMITTER: Lu Z 

PROVIDER: S-EPMC12921855 | biostudies-literature | 2026 Feb

REPOSITORIES: biostudies-literature