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Heterometal Dopant Changes the Mechanism of Proton-Coupled Electron Transfer at the Polyoxovanadate-Alkoxide Surface.

ABSTRACT: The transfer of two H-atom equivalents to the titanium-doped polyoxovanadate-alkoxide, [TiV5O6(OCH3)13], results in the formation of a V(III)-OH2 site at the surface of the assembly. Incorporation of the group (IV) metal ion results in a weakening of the O-H bonds of [TiV5O5(OH2)(OCH3)13] in comparison to its homometallic congener, [V6O6(OH2)(OCH3)12], resembling more closely the thermodynamics reported for the one-electron reduced derivative, [V6O6(OH2)(OCH3)12]1-. An analysis of early time points of the reaction of [TiV5O6(OCH3)13] and 5,10-dihydrophenazine reveals the formation of an oxidized substrate, suggesting that proton-coupled electron transfer proceeds via initial electron transfer from substrate to cluster prior to proton transfer. These results demonstrate the profound influence of heterometal dopants on the mechanism of PCET with respect to the surface of the assembly.

SUBMITTER: Cooney SE 

PROVIDER: S-EPMC10835708 | biostudies-literature | 2024 Jan

REPOSITORIES: biostudies-literature

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Heterometal Dopant Changes the Mechanism of Proton-Coupled Electron Transfer at the Polyoxovanadate-Alkoxide Surface.

Cooney Shannon E SE   Walls M Rebecca A MRA   Schreiber Eric E   Brennessel William W WW   Matson Ellen M EM  

Journal of the American Chemical Society 20240119 4

The transfer of two H-atom equivalents to the titanium-doped polyoxovanadate-alkoxide, [TiV<sub>5</sub>O<sub>6</sub>(OCH<sub>3</sub>)<sub>13</sub>], results in the formation of a V(III)-OH<sub>2</sub> site at the surface of the assembly. Incorporation of the group (IV) metal ion results in a weakening of the O-H bonds of [TiV<sub>5</sub>O<sub>5</sub>(OH<sub>2</sub>)(OCH<sub>3</sub>)<sub>13</sub>] in comparison to its homometallic congener, [V<sub>6</sub>O<sub>6</sub>(OH<sub>2</sub>)(OCH<sub>3</s  ...[more]

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