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A Highly Reactive Oxoiron(IV) Complex Supported by a Bioinspired N3O Macrocyclic Ligand

Title
A Highly Reactive Oxoiron(IV) Complex Supported by a Bioinspired N3O Macrocyclic Ligand
Authors
Monte Pérez I.Engelmann X.Lee Y.-M.Yoo M.Kumaran E.Farquhar E.R.Bill E.England J.Nam W.Swart M.Ray K.
Ewha Authors
남원우
SCOPUS Author ID
남원우scopus
Issue Date
2017
Journal Title
Angewandte Chemie - International Edition
ISSN
1433-7851JCR Link
Citation
vol. 56, no. 46, pp. 14384 - 14388
Keywords
hydrogen atom transferO ligandsoxoiron(IV) complexesoxygen atom transferspin state
Publisher
Wiley-VCH Verlag
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
The sluggish oxidants [FeIV(O)(TMC)(CH3CN)]2+ (TMC=1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) and [FeIV(O)(TMCN-d12)(OTf)]+ (TMCN-d12=1,4,7,11-tetra(methyl-d3)-1,4,7,11-tetraazacyclotetradecane) are transformed into the highly reactive oxidant [FeIV(O)(TMCO)(OTf)]+ (1; TMCO=4,8,12-trimethyl-1-oxa-4,8,12-triazacyclotetradecane) upon replacement of an NMe donor in the TMC and TMCN ligands by an O atom. A rate enhancement of five to six orders of magnitude in both H atom and O atom transfer reactions was observed upon oxygen incorporation into the macrocyclic ligand. This finding was explained in terms of the higher electrophilicity of the iron center and the higher availability of the more reactive S=2 state in 1. This rationalizes nature's preference for using O-rich ligand environments for the hydroxylation of strong C−H bonds in enzymatic reactions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
DOI
10.1002/anie.201707872
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자연과학대학 > 화학·나노과학전공 > Journal papers
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