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DOI: 10.1039/A701588G (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 2697-2704

Copper complexes of a p-phenylenediamine-based bis(tridentate) ligand[hair space]

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Thomas Buchen, Alan Hazell, Lars Jessen, Christine J. McKenzie, Lars Preuss Nielsen, Jens Z. Pedersen and Dieter Schollmeyer

Abstract

A new bis(tridentate) compound, N,N,N′,N′-tetrakis(2- pyridylmethyl)benzene-1,4-diamine (tpbd), its diprotonated derivative, [H2tpbd]2+, and a dicopper complex [Cu2(tpbd)(H2O)4][S2O 6]2 have been prepared and structurally characterized. The pyridyl nitrogen atoms are strongly hydrogen bonded in the crystal structure of the yellow diprotonated salt tpbd·2HClO4·2Me2CO. The bis(picolyl)amine ends of the ligand show a meridional-type co-ordination to the copper ions in the complex. Magnetic susceptibility measurements on [Cu2(tpbd)(H2O)4][S2O] 2 indicate that the p-phenylenediamine bridge commutes a weak antiferromagnetic coupling [J = -15.56(6) cm-1]. Two related dicopper complexes, Cu2(tpbd)Cl4 and Cu2(tpbd)(NO3)4, were also isolated. The ESR spectra of the chloride and nitrate complexes indicated negligible magnetic exchange coupling. Reaction of tpbd with one-electron oxidants generated a purple radical cation which has been characterized by ESR and UV/VIS spectroscopy.

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