Mixed-ligand copper(II) complexes with positive redox potentials

Abstract

Mixed-ligand complexes formed by reaction of Cu(ClO₄)₂ with 3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine (dppt) as primary ligand and 2,2'-bipyridine (bipy), 1,10-phenanthroline (phen), 2,9-dimethyl-1,10-phenanthroline (dmp), N,N-bis(pyrid-2-ylmethyl)amine (dipica), N,N-bis(benzimidazol-2-ylmethyl)amine (bba), 1,3-bis(2-benzimidazolyl)-2-thiapropane (bbms) and 1,5-bis(benzimidazolyl)-3-thiapentane (bbes) as the secondary ligands have been isolated. They are of the type [Cu(dppt)L](ClO₄)2·nH₂O, where n = 0 or 2. All complexes exhibit only one ligand field band and their cryogenic solution e.p.r. spectra are axial, with v_max and g_|| values diagnostic of a square-based geometry. The spectral and redox data are consistent with facial coordination of the tridentate ligands. All the complexes exhibit a positive redox potential (versus n.h.e.). The weak σ -bonding of dppt, caused by the highly electron-withdrawing phenyl rings, the strong π -back bonding involving phen and dmp, and interligand repulsions appear to be responsible for the relatively positive Cu^II/Cu^I redox potentials.