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The Mechanism of Stereospecific CH Oxidation by Fe(Pytacn) Complexes: Bioinspired Non-Heme Iron Catalysts Containing cis-Labile Exchangeable Sites

A detailed mechanistic study of the hydroxylation of alkane CH bonds using H2O2 by a family of mononuclear non heme iron catalysts with the formula [FeII(CF3SO3)2(L)] is described, in which L is a tetradentate ligand containing a triazacyclononane tripod and a pyridine ring bearing different substituents at the and positions, which tune the electronic or steric properties of the corresponding iron complexes. Two inequivalent cis-labile exchangeable sites, occupied by triflate ions, complete the octahedral iron coordination sphere. The CH hydroxylation mediated by this family of complexes takes place with retention of configuration. Oxygen atoms from water are incorporated into hydroxylated products and the extent of this incorporation depends in a systematic manner on the nature of the catalyst, and the substrate. Mechanistic probes and isotopic analyses, in combination with detailed density functional theory (DFT) calculations, provide strong evidence that CH hydroxylation is performed by highly electrophilic [FeV(O)(OH)L] species through a concerted asynchronous mechanism, involving homolytic breakage of the CH bond, followed by rebound of the hydroxyl ligand. The [FeV(O)(OH)L] species can exist in two tautomeric forms, differing in the position of oxo and hydroxide ligands. Isotopic-labeling analysis shows that the relative reactivities of the two tautomeric forms are sensitively affected by the substituent of the pyridine, and this reactivity behavior is rationalized by computational methods

Financial support for this work was provided by the Spanish Ministry of Science (Project CTQ2009-08464/BQU and Consolider Ingenio/CSD2010-00065 to M. C., Project CTQ2011-23156/BQU to J.M.L.) the European Research Council (ERC-2009-StG-239910 to M. C.), and US Department of Energy (DE-FG02-03ER15455 to LQ). M. C. and X. R. acknowledge Generalitat de Catalunya for ICREA Academia Awards and 2009-SGR637. A. C. acknowledges the European Commission for a Career Integration Grant (FP7-PEOPLE-2011-CIG-303522). The Spanish Ministry of Science is acknowledged for a FPU PhD grant to I. P., for a FPI PhD grant to V. P. and for a Ramon y Cajal contract to A. C. We thank Catexel for a generous gift of tritosyl-1,4,7-triazacyclononane

© Chemistry : a European Journal, 2013, vol. 19, núm. 21, p. 6724-6738

Wiley-VCH Verlag

Author: Prat Casellas, Irene
Company Casadevall, Anna
Postils, Verònica
Ribas Salamaña, Xavi
Que, Lawrence
Luis Luis, Josep Maria
Costas Salgueiro, Miquel
Date: 2013
Abstract: A detailed mechanistic study of the hydroxylation of alkane CH bonds using H2O2 by a family of mononuclear non heme iron catalysts with the formula [FeII(CF3SO3)2(L)] is described, in which L is a tetradentate ligand containing a triazacyclononane tripod and a pyridine ring bearing different substituents at the and positions, which tune the electronic or steric properties of the corresponding iron complexes. Two inequivalent cis-labile exchangeable sites, occupied by triflate ions, complete the octahedral iron coordination sphere. The CH hydroxylation mediated by this family of complexes takes place with retention of configuration. Oxygen atoms from water are incorporated into hydroxylated products and the extent of this incorporation depends in a systematic manner on the nature of the catalyst, and the substrate. Mechanistic probes and isotopic analyses, in combination with detailed density functional theory (DFT) calculations, provide strong evidence that CH hydroxylation is performed by highly electrophilic [FeV(O)(OH)L] species through a concerted asynchronous mechanism, involving homolytic breakage of the CH bond, followed by rebound of the hydroxyl ligand. The [FeV(O)(OH)L] species can exist in two tautomeric forms, differing in the position of oxo and hydroxide ligands. Isotopic-labeling analysis shows that the relative reactivities of the two tautomeric forms are sensitively affected by the substituent of the pyridine, and this reactivity behavior is rationalized by computational methods
Financial support for this work was provided by the Spanish Ministry of Science (Project CTQ2009-08464/BQU and Consolider Ingenio/CSD2010-00065 to M. C., Project CTQ2011-23156/BQU to J.M.L.) the European Research Council (ERC-2009-StG-239910 to M. C.), and US Department of Energy (DE-FG02-03ER15455 to LQ). M. C. and X. R. acknowledge Generalitat de Catalunya for ICREA Academia Awards and 2009-SGR637. A. C. acknowledges the European Commission for a Career Integration Grant (FP7-PEOPLE-2011-CIG-303522). The Spanish Ministry of Science is acknowledged for a FPU PhD grant to I. P., for a FPI PhD grant to V. P. and for a Ramon y Cajal contract to A. C. We thank Catexel for a generous gift of tritosyl-1,4,7-triazacyclononane
Format: application/pdf
ISSN: 0947-6539 (versió paper)
1521-3765 (versió electrònica)
Document access: http://hdl.handle.net/10256/8667
Language: eng
Publisher: Wiley-VCH Verlag
Collection: MICINN/PN 2010-2012/CTQ2009-08464
MICINN/PN 2010-2016/CSD2010-00065
MICINN/PN 2012-2014/CTQ2011-23156
AGAUR/2009-2014/2009 SGR-637
Reproducció digital del document publicat a: http://dx.doi.org/10.1002/chem.201300110
Articles publicats (D-Q)
info:eu-repo/grantAgreement/EC/FP7/303522
info:eu-repo/grantAgreement/EC/FP7/239910
Is part of: © Chemistry : a European Journal, 2013, vol. 19, núm. 21, p. 6724-6738
Rights: Tots els drets reservats
Subject: Catalitzadors metàl·lics de transició
Transition metal catalysts
Química bioinorgànica
Bioinorganic chemistry
Funcional de densitat, Teoria del
Density functionals
Oxidació
Oxidation
Title: The Mechanism of Stereospecific CH Oxidation by Fe(Pytacn) Complexes: Bioinspired Non-Heme Iron Catalysts Containing cis-Labile Exchangeable Sites
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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