Mononuclear and Polynuclear Copper(II) Complexes Derived from Pyridylalkylaminomethylphenol Polypodal Ligands
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.
Más información
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 |