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Copper(II) complexes with new polypodal ligands presenting axial-equatorial phenoxo bridges {2-[(Bis(2-pyridylmethyl)amino)methyl]-4-methyl phenol, 2-[(Bis(2-pyr1dylmethyl)amino)methyl]-4-methyl-6-(methylthio)phenol}: Examples of ferromagnetically coupled Bi- and trinuclear copper(II) complexes

Authordc.contributor.authorManzur Saffie, Jorge es_CL
Authordc.contributor.authorMora, Hector es_CL
Authordc.contributor.authorVega, Andrés es_CL
Authordc.contributor.authorSpodine Spiridonova, Evgenia es_CL
Authordc.contributor.authorVenegas Yazigi, Diego es_CL
Authordc.contributor.authorGarland, María Teresa es_CL
Authordc.contributor.authorEl Fallah, M. Salah es_CL
Authordc.contributor.authorEscuer, Albert 
Admission datedc.date.accessioned2009-06-01T11:54:33Z
Available datedc.date.available2009-06-01T11:54:33Z
Publication datedc.date.issued2007-08
Cita de ítemdc.identifier.citationINORGANIC CHEMISTRY, v: 46, issue: 17, p.: 6924-6932, AUG 20, 2007en
Identifierdc.identifier.issn0020-1669
Identifierdc.identifier.urihttp://repositorio.uchile.cl/handle/2250/124950
Abstractdc.description.abstractTwo new ligands, 2-[(bis(2-pyridylmethyl)amino)methyl]-4-methylphenol (HL) and 2-[(bis(2-pyridylmethyl)amino)methyl]- 4-methyl-6-(methylthio)phenol (HSL), were synthesized and were used to prepare the trinuclear copper(II) complex {- [CuSL(Cl)]2Cu}(PF6)2·H2O (1) and the corresponding binuclear complexes [Cu2(SL)2](PF6)2 (2) and [Cu2L2](PF6)2 (3). The crystal structure of 1 shows two different coordination environments: two square base pyramidal centers (Cu1 and Cu1a, related by a C2 axes), acting as ligands of a distorted square planar copper center (Cu2) by means of the sulfur atom of the SCH3 substituent and the bridging phenoxo oxygen atom of the ligand (Cu2-S ) 2.294 …). Compounds 2 and 3 show two equivalent distorted square base pyramidal copper(II) centers, bridged in an axial-equatorial fashion by two phenoxo groups, thus defining an asymmetric Cu2O2 core. A long copper-sulfur distance measured in 2 (2.9261(18) …) suggests a weak bonding interaction. This interaction induces a torsion angle between the methylthio group and the phenoxo plane resulting in a dihedral angle of 41.4(5)°. A still larger distortion is observed in 1 with a dihedral angle of 74.0(6)°. DFT calculations for 1 gave a ferromagnetic exchange between first neighbors interaction, the calculated J value for this interaction being +11.7 cm-1. In addition, an antiferromagnetic exchange for 1 was obtained for the second neighbor interaction with a J value of -0.05 cm-1. The Bleaney-Bowers equation was used to fit the experimental magnetic susceptibility data for 2 and 3; the best fit was obtained with J values of +3.4 and -16.7 cm-1, respectively. DFT calculations for 2 and 3 confirm the nature and the values of the J constants obtained by the fit of the experimental data. ESR and magnetic studies on the reported compounds show a weak exchange interaction between the copper(II) centers. The low values obtained for the coupling constants can be explained in terms of a poor overlap between the magnetic orbitals, due to the axial-equatorial phenoxo bridging mode observed in these complexes.en
Patrocinadordc.description.sponsorshipFinancial support from Project FONDECYT 1050484 is gratefully acknowledged. Support from grants given by the Ministerio de Educación y Ciencia de España (Programa Ramón y Cajal) and BQU2003/00538 is also gratefully acknowledged. E.S. and D.V.-Y. acknowledge FONDAP 11980002 and Proyecto Bicentenario de Inserción Académica for financial support.en
Lenguagedc.language.isoenen
Publisherdc.publisherAMER CHEMICAL SOCen
Keywordsdc.subjectTRANSITION-METAL-COMPLEXESen
Títulodc.titleCopper(II) complexes with new polypodal ligands presenting axial-equatorial phenoxo bridges {2-[(Bis(2-pyridylmethyl)amino)methyl]-4-methyl phenol, 2-[(Bis(2-pyr1dylmethyl)amino)methyl]-4-methyl-6-(methylthio)phenol}: Examples of ferromagnetically coupled Bi- and trinuclear copper(II) complexesen
Document typedc.typeArtículo de revistaen


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