Triggering the generation of an iron(IV)-oxo compound and its reactivity toward sulfides by RuII photocatalysis
dc.contributor.author
dc.date.accessioned
2015-05-04T07:22:20Z
dc.date.available
2015-05-04T07:22:20Z
dc.date.issued
2014
dc.identifier.issn
0002-7863
dc.identifier.uri
dc.description.abstract
The preparation of [FeIV(O)(MePy2tacn)]2+ (2, MePy2tacn = N-methyl-N,N-bis(2-picolyl)-1,4,7-triazacyclononane) by reaction of [FeII(MePy2tacn)(solvent)]2+ (1) and PhIO in CH3CN and its full characterization are described. This compound can also be prepared photochemically from its iron(II) precursor by irradiation at 447 nm in the presence of catalytic amounts of [Ru II(bpy)3]2+ as photosensitizer and a sacrificial electron acceptor (Na2S2O8). Remarkably, the rate of the reaction of the photochemically prepared compound 2 toward sulfides increases 150-fold under irradiation, and 2 is partially regenerated after the sulfide has been consumed; hence, the process can be repeated several times. The origin of this rate enhancement has been established by studying the reaction of chemically generated compound 2 with sulfides under different conditions, which demonstrated that both light and [Ru II(bpy)3]2+ are necessary for the observed increase in the reaction rate. A combination of nanosecond time-resolved absorption spectroscopy with laser pulse excitation and other mechanistic studies has led to the conclusion that an electron transfer mechanism is the most plausible explanation for the observed rate enhancement. According to this mechanism, the in-situ-generated [RuIII(bpy)3] 3+ oxidizes the sulfide to form the corresponding radical cation, which is eventually oxidized by 2 to the corresponding sulfoxide
dc.description.sponsorship
We acknowledge the European Commission for projects FP7-PEOPLE-2011-CIG-303522 (A.C.), FP7-PEOPLE-2010-ERG-268445 (J.L.-F.), FP7-PEOPLE-CIG-303522 (M.G.B.), and ERC-009StG-239910 (MC.); the Spanish Ministry of Science for Projects CTQ2012-37420-C02-01/BQU (MC.), CSD2010-00065 (MC.), and CTQ2011-27758 (J.P.P.); Generalitat de Catalunya for an ICREA Academia Award and Project 2009-SGR637 (M.C.); and Generalitat Valenciana for Project ACOMP/2013/008 (J.P.P.). The Spanish Ministry of Science is acknowledged for a Ramon y Cajal contract to A.C. and J.L.-F. J.M.L. acknowledges the support, in part, of Labex ARCANE (ANR-11-LABX-0003-01). The work at the University of Minnesota was supported by the US National Science Foundation (Grant CHE1058248 to L.Q) and the Dr. Venkateswarlu Pothapragada and Family Fellowship (to M.P.). XAS data were collected at beamline 9-3 of the Stanford Synchrotron Radiation Lightsource supported by the US-NIH and US-DOE. We thank Catexel for a generous gift of tritosyl-1,4,7-triazacyclononane
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
American Chemical Society (ACS)
dc.relation
info:eu-repo/grantAgreement/MINECO//CTQ2012-37420-C02-01/ES/DISEÑO BIOINSPIRADO DE CATALIZADORES PARA LA OXIDACION DE ENLACES C-H, C=C Y AGUA/
MICINN/PN 2010-2016/CSD2010-00065
AGAUR/2009-2014/2009 SGR-637
dc.relation.isformatof
Reproducció digital del document publicat a: http://dx.doi.org/10.1021/ja412059c
dc.relation.ispartof
© Journal of the American Chemical Society, 2014, vol. 136, p. 4624-4633
dc.relation.ispartofseries
Articles publicats (D-Q)
dc.rights
Tots els drets reservats
dc.subject
dc.title
Triggering the generation of an iron(IV)-oxo compound and its reactivity toward sulfides by RuII photocatalysis
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/embargoedAccess
dc.embargo.terms
Cap
dc.date.embargoEndDate
info:eu-repo/date/embargoEnd/2026-01-01
dc.relation.projectID
info:eu-repo/grantAgreement/EC/FP7/303522/EU/Key insights into oxidation chemistry through synthetic systems: N2O activation with first-row transition-metals and O2 activation in heterobimetallic Fe-Ni systems/NEWOXMET
info:eu-repo/grantAgreement/EC/FP7/268445/EU/Modular Ligands for Water Splitting/WATERSPLIT
info:eu-repo/grantAgreement/EC/FP7/239910/EU/Bio-inspired Design of Catalysts for Selective Oxidations of C-H and C=C Bonds/BIDECASEOX
dc.type.version
info:eu-repo/semantics/publishedVersion
dc.identifier.doi
dc.identifier.idgrec
020944
dc.contributor.funder
dc.relation.ProjectAcronym
dc.identifier.eissn
1520-5126