Mononuclear and Polynuclear Copper(II) Complexes Derived from Pyridylalkylaminomethylphenol Polypodal Ligands

Manzur, J.; Mora, H.; Vega A.; Venegas-Yazigi, D; Novak MA.; Sabino, JR; Paredes-Garcia, V; Spodine, E.

Abstract

Four mononuclear complexes [Cu(HL1)CI]PF6-CH 3OH (1), [Cu(HSL1)CI]PF6-0.75H2O (2), [Cu(HL2)CI]PF6-CH3- OH (3), [Cu(HSL 2)CI]PF6-1.5CH3OH (4), and two polynuclear complexes [Cu2(SL2)2](PF6) 2-2CH3OH (5) and {Cu[Cu(SL2)(CI)] 2}(PF6)2 (6) (HL1: 2-[(bis(2-pyridylmethyl)-amino)methyl]-4-methylphenol; HSL1: 2-[(bis(2-pyridylmethyl)amino) methyl]-4-methyl-6-(methyl-thio)phenol; HL 2: 2-[(2-pyridylmethyl)(2'-pyridylethyl)-aminomethyl)]-4- methylphenol; HSL2: 2-[(2-pyridylmethyl)(2'-pyridylethyl)amino- methyl]-4-methyl-6-(metnylthio)phenol were obtained and characterized. The crystal structures of the mononuclear complexes 1 -4 show the copper centers in a square-base pyramidal environment with the phenolic oxygen coordinated at the axial position. Dinuclear complex 5 has two copper centers with different geometry and bridged by phenoxo oxygens; one of the copper atoms is square pyramidal while the other can be described with a highly distorted octahedral geometry with a long Cu-S distance (2.867 Å). Density functional theory calculations were used to obtain the reported structure of 6, since single crystals suitable for X-ray diffraction were not isolated. Magnetic studies done for 5 and 6 show an antiferromagnetic behavior for 5 (J =-134 cm -1) and a ferromagnetic behavior for 6 (J = +11.9 cm-1). Redox potentials for the mononuclear complexes were measured by cyclic voltammetry; the values show the effect of the chelating ring size (-213 mV and -142 mV for Cu-HL1 and Cu-HL2, respectively) and the presence of the thiomethyl substituent (-213 mV and -184 mV for Cu-HL1 and Cu-HSL1, respectively). © 2009 American Chemical Society.

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Título según WOS: Mononuclear and Polynuclear Copper(II) Complexes Derived from Pyridylalkylaminomethylphenol Polypodal Ligands
Título según SCOPUS: Mononuclear and polynuclear copper(II) complexes derived from pyridylalkylaminomethylphenol polypodal ligands
Título de la Revista: INORGANIC CHEMISTRY
Volumen: 48
Número: 18
Editorial: American Chemical Society
Fecha de publicación: 2009
Página de inicio: 8845
Página final: 8855
Idioma: English
URL: http://pubs.acs.org/doi/abs/10.1021/ic901026x
DOI:

10.1021/ic901026x

Notas: ISI, SCOPUS