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Structural modeling of iron halogenases: Synthesis and reactivity of halide-iron(iv)-oxo compounds

A structural synthetic model of the iron(IV)-oxo-halide active species of non-heme iron dependent halogenases is reported. Compounds with general formula [FeIV(O)(X)(Pytacn)]+ (1-X, X = Cl, Br) have been prepared and characterized spectroscopically and chemically with regard to their oxidizing ability. 1-X performs hydrogen-atom abstraction of C–H bonds at reaction rates 2–3 times faster than the corresponding solvato dicationic species, thus modelling the first step in C–H functionalization taking place in natural halogenation

The authors acknowledge the European Commission for project FP7-PEOPLE-2011-CIG-303522 (A.C.), the European Research Council for project ERC-009StG-239910 (M.C.), Generalitat de Catalunya for an ICREA Academia Award (M.C.) and a predoctoral FI fellowship to O.P., and the SpanishMinistry of Science for project CTQ2012-37420-C02-01/BQU (M.C.) and a Ramon y Cajal contract to A.C. J.-M.L. acknowledges the support, in part, of Labex ARCANE (ANR-11-LABX-0003-01). We thank Catexel for a generous gift of tritosyl-1,4,7-triazacyclononane. We are grateful for financial support from INNPLANTA project INP-2011-0059-PCT-420000-ACT1 to Dr X. Ribas

© Chemical Communications, 2014, vol. 50, p. 10887-10890

Royal Society of Chemistry (RSC)

Author: Planas Fàbrega, Oriol
Clémancey, Martin
Latour, Jean Marc
Company Casadevall, Anna
Costas Salgueiro, Miquel
Date: 2014 July 22
Abstract: A structural synthetic model of the iron(IV)-oxo-halide active species of non-heme iron dependent halogenases is reported. Compounds with general formula [FeIV(O)(X)(Pytacn)]+ (1-X, X = Cl, Br) have been prepared and characterized spectroscopically and chemically with regard to their oxidizing ability. 1-X performs hydrogen-atom abstraction of C–H bonds at reaction rates 2–3 times faster than the corresponding solvato dicationic species, thus modelling the first step in C–H functionalization taking place in natural halogenation
The authors acknowledge the European Commission for project FP7-PEOPLE-2011-CIG-303522 (A.C.), the European Research Council for project ERC-009StG-239910 (M.C.), Generalitat de Catalunya for an ICREA Academia Award (M.C.) and a predoctoral FI fellowship to O.P., and the SpanishMinistry of Science for project CTQ2012-37420-C02-01/BQU (M.C.) and a Ramon y Cajal contract to A.C. J.-M.L. acknowledges the support, in part, of Labex ARCANE (ANR-11-LABX-0003-01). We thank Catexel for a generous gift of tritosyl-1,4,7-triazacyclononane. We are grateful for financial support from INNPLANTA project INP-2011-0059-PCT-420000-ACT1 to Dr X. Ribas
Format: application/pdf
ISSN: 1359-7345 (versió paper)
1364-548X (versió electrònica)
Document access: http://hdl.handle.net/10256/10913
Language: eng
Publisher: Royal Society of Chemistry (RSC)
Collection: MINECO/PN 2013-2015/CTQ2012-37420-C02-01
MICINN/PN 2011/INP-2011-0059-PCT-420000
Reproducció digital del document publicat a: http://dx.doi.org/10.1039/c4cc03234a
Articles publicats (D-Q)
info:eu-repo/grantAgreement/EC/FP7/303522
info:eu-repo/grantAgreement/EC/FP7/239910
Is part of: © Chemical Communications, 2014, vol. 50, p. 10887-10890
Rights: Tots els drets reservats
Subject: Ferro -- Compostos
Iron compounds
Oxidació
Oxidation
Title: Structural modeling of iron halogenases: Synthesis and reactivity of halide-iron(iv)-oxo compounds
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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