Design of dinuclear copper species with carboranylcarboxylate ligands: study of their steric and electronic effects
dc.contributor.author
dc.date.accessioned
2015-12-15T09:10:12Z
dc.date.available
2015-12-15T09:10:12Z
dc.date.issued
2011-11-18
dc.identifier.issn
0947-6539
dc.identifier.uri
dc.description.abstract
A series of new mononuclear and carboranylcarboxylate-bridged dinuclear copper(II) compounds containing the 1-CH3-2-CO2H-1,2- closo-C2B10H10 carborane ligand (LH) has been synthesized. Reaction of different copper salts with LH at room temperature leads to dinuclear compounds of the general formula [Cu2(μ-L) 4(Lt)2] (Lt=thf (1), L t=H2O (1′)). The reaction of 1 and 1′ with different terminal pyridyl (py) ligands leads to the formation of a series of structurally analogous complexes by substitution of the terminal ligand thf or H2O (Lt=py (2), p-CF3-py (3), p-CH 3-py (4), pz (6), and 4,4′-bpy (7)), which maintain the structural Cu2(μ-O2CR)4 core in the majority of the cases except for o-(CH3)2-py, where a mononuclear compound (5) is exclusively obtained. These compounds have been characterized through analytical, spectroscopic (NMR, IR, UV-visible, ESI-MS) and magnetic techniques. X-ray structural analysis revealed a paddle-wheel structure for the dinuclear compounds, with a square-pyramidal geometry around each copper ion and the carboranylcarboxylate ions bridging two copper atoms in syn-syn mode. The mononuclear complex obtained with the o-(CH3)2-py ligand presents a square-planar structure, in which the carboranylcarboxylate ligand adopts a monodentate coordination mode. The magnetic properties of the dinuclear compounds 1, 3, 4, and 6 show a strong antiferromagnetic coupling in all cases (J=-261 (1), -255 (3), -241 (4), -249 cm-1 (6)). Computational studies based on hybrid density functional methods have been used to study the magnetic properties of the complexes and also to evaluate their relative stability on the basis of the strength of the bond between each CuII and the terminal ligand
dc.description.sponsorship
This research has been financed by MEC of Spain through projects CTQ2010-21532-C02-01 and CTQ2010-16237 and Generalitat de Catalunya (2009/SGR/00279). M.F. thanks Generalitat de Catalunya for an FI predoctoral grant and A.R.P. to the Spanish Ministry of Education for the FPU grant. The access to the computational facilities of High Performance Computing Centre of CSIC and Centre de Supercomputaci de Catalunya (CESCA) is gratefully acknowledged. Serveis T cnics de Recerca (STR) from UdG are also acknowledged for technical support. N.A.-A. thanks the Spanish Ministerio de Ciencia e Innovaci n (CTQ2009-06959) and ICREA (Instituci Catalana de Recerca i Estudis Avançats). E.R. thanks to the Ministerio de Ciencia e Innovaci n and the Direcci General de Recerca for the grants CTQ2008-06670-C02-01 and 2009SGR-1459 as well as to the Centre de Supercomputaci de Catalunya (CESCA) for providing computational resources
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
Wiley-VCH Verlag
dc.relation
info:eu-repo/grantAgreement/MICINN//CTQ2010-21532-C02-01/ES/MIMETIZACION DE PROCESOS BIOINORGANICOS Y APLICACIONES CATALITICAS CON COMPUESTOS DE METALES DE TRANSICION./
AGAUR/2009-2014/2009 SGR-279
dc.relation.isformatof
Reproducció digital del document publicat a: http://dx.doi.org/10.1002/chem.201101929
dc.relation.ispartof
© Chemistry - A European Journal, 2011, vol. 17, núm. 47, p. 13217-13229
dc.relation.ispartofseries
Articles publicats (D-Q)
dc.rights
Tots els drets reservats
dc.subject
dc.title
Design of dinuclear copper species with carboranylcarboxylate ligands: study of their steric and electronic effects
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.type.version
info:eu-repo/semantics/publishedVersion
dc.identifier.doi
dc.identifier.idgrec
018605
dc.contributor.funder
dc.relation.ProjectAcronym
dc.identifier.eissn
1521-3765