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Oxyl radical required for o-o bond formation in synthetic Mn-catalyst

Oxyl radical required for o-o bond formation in synthetic Mn-catalyst

Inorganic Chemistry 43(1): 264-274

DFT calculations using the B3LYP functional support the suggestion that the [(terpy)(H(2)O)Mn(IV)(micro-O)(2)Mn(III)(H(2)O)(terpy)](3+) (terpy=2,2':6,2' '-terpyridine) complex functions as a synthetic O(2) catalyst. The calculated barrier for O-O bond formation with water is 23 kcal/mol. In this complex, as well as in models of the oxygen evolving complex in PSII, the active species is a Mn(IV)-oxyl radical. From comparisons with inactive Mn(V)-oxo complexes, it is proposed that radical formation is actually a requirement for O(2) formation activity in Mn-complexes.

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Accession: 049839228

Download citation: RISBibTeXText

PMID: 14704076

DOI: 10.1021/ic0348188

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