To date Co4O4(py)4(OAc)4 (1  ) has been demonstrated to be an active wateroxidation catalyst using a standard solution based photoassay. However the natureof the catalytic mechanism remains unclear. To shed light on the mechanism, weinvestigated the role of metal Co nuclearity in the catalytic activity of pyridine-acetate CoxOy complexes. We report the synthesis, catalytic activity and lifetimes ofdinuclear and trinuclear �incomplete cubanes� [(py)4Co2(OAc)3(OH)2]3+ (2  ), [(py)5Co3O(OAc)3(OH)2 2+] (3  ), and compare to the complete cubane (1  ). We find thatmetal nuclearity plays a decisive role both for material stability and catalytic activityof these complexes, with the Co4O4 cubane core of (1  ) being the only stable catalyst.Supported by AFOSR FA9550-11-1-0231.

Examining the relationship between cluster nuclearity and catalytic activity for water oxidation in molecular cobalt complexes

245th National Meeting (2013)

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