Models for Copper-Dioxygen Complexes: the Chemistry of Copper(II) with Some Planar Tridentate Nitrogen Ligands

Article abstract of DOI:10.1002/hlca.19890720218

The solution chemistry of Cu(II) with a series of five planar tridentate nitrogen ligands, 2,6-bis(benzimidazol-2-yl)pyridine (bzimpy, 1), 2,6-bis(1-methylbenzimidazol-2-yl)pyridine (mbzimpy, 2), 2,6-bis(benzothiazol-2-yl)pyridine (bzthpy, 3), 2,6-bis(benzoxazol-2-yl)pyridine (bzoxpy, 4), and 2,2',6',2"-terpyridyl (terpy, 5) is reported.Electronic and EPR spectra are consistent with the complexes ²⁺ having essentially tetragonal structure in solution, with the fourth coordination site in the plane of the ligand occupied by solvent. bzthpy and bzoxpy show smaller ligand-field splittings than bzimpy, mbzimpy, and terpy, and are easily decomplexed from the copper.Substitution of the coordinated solvent molecule in the plane of the ligand is observed with Cl^- and OH^- (provided that the ligand has no acidic protons) for all ligands except terpy.The reaction between ²⁺ and imidazole has been studied by potentiometric titration in MeCN/H2O 1:1 and shows strong binding of the imidazole in the plane (log K = 4.5 at 25 deg C), and also the formation of an imidazolate-bridged dinuclear species.