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Selective Photoproduction of O2 from the Mn4 O4 Cubane Core: A Structural and Functional Model for the Photosynthetic
Masayuki Yagi1, Kurt V Wolf1, Patrick J Baesjou1
1Department of Chemistry Princeton University Princeton, NJ, 08544-1009, NJ (USA) Fax: (+1) 609-258-1980.
Abstract:
Cores for thought! A new [Mn4 O4 ]6+ "cubane" core complex (L6 Mn4 O4 ) with six facially bridging phosphinate chelate ligands (L- =(MePh)2 PO2- ) was synthesized. Photo-excitation releases molecular O2 by intramolecular coupling of two core oxygen atoms and selective rearrangement to a [Mn4 O2 ]6+ "butterfly" core ([L5 Mn4 O2 ]+ ; see scheme). Thus the Mn4 O4 cubane core exhibits unique reactivity in O2 evolution which may account for its presence in the photosynthetic enzyme.
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