The new crystal structure of  the Photosystem II oxygen evolving complex (OEC) has breathed new life into synthetic model chemistry. Across the subdiscipline of Mn-O cluster chemistry, new, highly relevant structural models have been reported in the past year. Traditionally, synthetic Mn-O clusters contain 6-coordinate Mn with terminal multidentate ligands. Structural changes in the OEC during turnover, including the possibility of lower-coordinate states have inspired our group to explore the chemistry of labile unchelated clusters of reduced coordination number. Our recent findings will be presented, which include structures of potential biological relevance, including a one-of-a-kind 5-coordinate, unchelated Mn-O cluster, clusters with �pinned butterfly� geometry, and heterocubane clusters with pendant Mn=X moieties (X = N, O) mimicking a proposed oxygen evolving S4 state of the OEC. Strucutre, and characterization will be presented, and the diverse reactivity of unchelated systems will be discussed.

Photosystem-II-inspired synthesis of unchelated manganese clusters of reduced coordination number

244th National Meeting (2012)

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