Regeneration and Degradation in a Biomimetic Polyoxometalate Water Oxidation Catalyst

[Image: see text] Complete understanding of catalytic cycles is required to advance the design of water oxidation catalysts, but it is difficult to attain, due to the complex factors governing their reactivity and stability. In this study, we investigate the regeneration and degradation pathways of the highly active biomimetic water oxidation catalyst [Mn(3+)(2)Mn(4+)(2)V(4)O(17)(OAc)(3)](3–), thereby completing its catalytic cycle. Beginning with the deactivated species [Mn(3+)(4)V(4)O(17)(OAc)(2)](4–) left over after O(2) evolution, we scrutinize a network of reaction intermediates belonging to two alternative water oxidation cycles. We find that catalyst regeneration to the activated species [Mn(4+)(4)V(4)O(17)(OAc)(2)(OH)(H(2)O)](−) proceeds via oxidation of each Mn center, with one water ligand being bound during the first oxidation step and a second water ligand being bound and deprotonated during the final oxidation step. ΔΔG values for this last oxidation are consistent with previous experimental results, while regeneration within an alternative catalytic cycle was found to be thermodynamically unfavorable. Extensive in silico sampling of catalyst structures also revealed two degradation processes: cubane opening and ligand dissociation, both of which have low barriers at highly reduced states of the catalyst due to the presence of Jahn–Teller effects. These mechanistic insights are expected to spur the development of more efficient and stable Mn cubane water oxidation catalysts.