Abstract
The transfer of two H-atom equivalents to the titanium-doped polyoxovanadate-alkoxide, [TiV(5)O(6)(OCH(3))(13)], results in the formation of a V(III)-OH(2) 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(5)O(5)(OH(2))(OCH(3))(13)] in comparison to its homometallic congener, [V(6)O(6)(OH(2))(OCH(3))(12)], resembling more closely the thermodynamics reported for the one-electron reduced derivative, [V(6)O(6)(OH(2))(OCH(3))(12)](1-). An analysis of early time points of the reaction of [TiV(5)O(6)(OCH(3))(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.