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Intrinsic properties and reactivities of mononuclear nonheme iron-oxygen complexes bearing the tetramethylcyclam ligand

Title
Intrinsic properties and reactivities of mononuclear nonheme iron-oxygen complexes bearing the tetramethylcyclam ligand
Authors
de Visser S.P.Rohde J.-U.Lee Y.-M.Cho J.Nam W.
Ewha Authors
남원우조재흥이용민
SCOPUS Author ID
남원우scopus; 이용민scopusscopus
Issue Date
2013
Journal Title
Coordination Chemistry Reviews
ISSN
0010-8545JCR Link
Citation
vol. 257, no. 2, pp. 381 - 393
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
Iron-oxygen species, such as iron(IV)-oxo, iron(III)-superoxo, iron(III)-peroxo, and iron(III)-hydroperoxo complexes, are key intermediates often detected in the catalytic cycles of dioxygen activation by heme and nonheme iron enzymes. Our understanding of the chemistry of these key intermediates has improved greatly by studies of the structural and spectroscopic properties and reactivities of their synthetic analogues. One class of biomimetic coordination complexes that has proven to be particularly versatile in studying dioxygen activation by metal complexes is comprised of Fe IVO and Fe IIIO 2(H) complexes of the macrocyclic tetramethylcyclam ligand (TMC, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane). Several recent advances have been made in the synthesis and isolation of new iron-oxygen complexes of this ligand, their structural and spectroscopic characterization, and elucidation of their reactivities in various oxidation reactions. In this review, we summarize the chemistry of the first structurally characterized mononuclear nonheme iron(IV)-oxo complex, in which the Fe IVO group was stabilized by the TMC ligand. Complexes with different axial ligands, [Fe IV(O)(TMC)(X)] n+, and complexes of other cyclam ligands are discussed as well. Very recently, significant progress has also been reported in the area of other iron-oxygen intermediates, such as iron(III)-superoxo, iron(III)-peroxo, and iron(III)-hydroperoxo complexes bearing the TMC ligand. The present results demonstrate how synthetic and mechanistic developments in biomimetic research can advance our understanding of dioxygen activation occurring in mononuclear nonheme iron enzymes. © 2012 Elsevier B.V..
DOI
10.1016/j.ccr.2012.06.002
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자연과학대학 > 화학·나노과학전공 > Journal papers
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