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Ministerio de EconomÃa y Competitividad (Espanya) | |
Serrano Plana, Joan
Costas Salgueiro, Miquel Company Casadevall, Anna |
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2014 | |
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 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 |
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application/pdf | |
http://hdl.handle.net/10256/10331 | |
eng | |
American Chemical Society (ACS) | |
info:eu-repo/semantics/altIdentifier/doi/10.1021/ic501951f info:eu-repo/semantics/altIdentifier/issn/0020-1669 info:eu-repo/semantics/altIdentifier/eissn/1520-510X MICINN/PN 2010-2016/CSD2010-00065 MICINN/PN 2011/INP-2011-0059-PCT-420000 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 |
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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/ | |
Tots els drets reservats | |
Lligands
Ligands Reaccions quÃmiques Chemical reactions Coure -- Compostos Copper compounds |
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Building complexity in O2-binding copper complexes: site-selective metalation and intermolecular O2-binding at dicopper and heterometallic complexes derived from an unsymmetric ligand | |
info:eu-repo/semantics/article | |
DUGiDocs |