Building complexity in O2-binding copper complexes: site-selective metalation and intermolecular O2-binding at dicopper and heterometallic complexes derived from an unsymmetric ligand
dc.contributor.author
dc.date.accessioned
2015-05-04T06:23:59Z
dc.date.available
2015-05-04T06:23:59Z
dc.date.issued
2014
dc.identifier.issn
0020-1669
dc.identifier.uri
dc.description.abstract
A novel unsymmetric dinucleating ligand (LN3N4) combining a tridentate and a tetradentate binding sites linked through a m-xylyl spacer was synthesized as ligand scaffold for preparing homo- and dimetallic complexes, where the two metal ions are bound in two different coordination environments. Site-selective binding of different metal ions is demonstrated. LN3N4 is able to discriminate between CuI and a complementary metal (M′ = CuI, ZnII, FeII, CuII, or GaIII) so that pure heterodimetallic complexes with a general formula [CuIM′(LN3N4)]n+ are synthesized. Reaction of the dicopper(I) complex [CuI 2(LN3N4)]2+ with O2 leads to the formation of two different copper-dioxygen (Cu2O2) intermolecular species (O and TP) between two copper atoms located in the same site from different complex molecules. Taking advantage of this feature, reaction of the heterodimetallic complexes [CuM′(LN3N4)]n+ with O2 at low temperature is used as a tool to determine the final position of the CuI center in the system because only one of the two Cu2O2 species is formed
dc.description.sponsorship
Financial support for this work was provided by the European Commission (FP7-PEOPLE-2011-CIG-303522 to A.C. and ERC-2009-StG-239910 to M.C.), MINECO (CTQ2012-37420-C02-01/BQU and CSD2010-00065 to M.C.) and Generalitat de Catalunya (ICREA Academia Award to M.C.). The Spanish Ministry of Science is acknowledged for a Ramon y Cajal contract to A.C. We are thankul to Dr. X. Ribas for financial support from INNPLANTA Project No. INP-2011-0059-PCT-420000-ACT1. We also thank Dr. L. Gomez (Serveis Tecnics de Recerca, Universitat de Girona) for helpful advice in setting up the HR-MS experiments and for fruitful discussions. We thank Catexel for a generous gift of 1,4,7-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
MICINN/PN 2011/INP-2011-0059-PCT-420000
dc.relation.isformatof
Reproducció digital del document publicat a: http://dx.doi.org/10.1021/ic501951f
dc.relation.ispartof
© Inorganic Chemistry, 2014, vol. 53, p. 12929-12938
dc.relation.ispartofseries
Articles publicats (D-Q)
dc.rights
Tots els drets reservats
dc.subject
dc.title
Building complexity in O2-binding copper complexes: site-selective metalation and intermolecular O2-binding at dicopper and heterometallic complexes derived from an unsymmetric ligand
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/FP7/239910/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
022148
dc.contributor.funder
dc.relation.ProjectAcronym
dc.identifier.eissn
1520-510X