Oxyl radical required for O-O bond formation in synthetic Mn-catalyst
2004 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 43, no 1, 264-274 p.Article in journal (Refereed) Published
DFT calculations using the B3LYP functional support the suggestion that the [(terpy)(H2O)Mn-IV(mu-O)(2)Mn-III(H2O)-(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.
Place, publisher, year, edition, pages
2004. Vol. 43, no 1, 264-274 p.
IdentifiersURN: urn:nbn:se:uu:diva-145464DOI: DOI: 10.1021/ic0348188PubMedID: 14704076OAI: oai:DiVA.org:uu-145464DiVA: diva2:396515