A wine red copper(II) complex of a tetradentate nitrogen donor showing two-electron oxidation. Generation of a copper(II)-phosphine bond

Abstract

Using the 1 : 2 condensate of benzil and 2-hydrazinopyridine as the ligand LH2 (H: dissociable NH proton), the red complex Cu(LH2)(ClO4)2 (1) was synthesized. The ligand also afforded the orange [Zn(LH2)(OH2)2](ClO4)2 (2). The X-ray crystal structures of the ligand, 1 and 2 have been determined. The metals in 1 and 2 have octahedral N4O2 environments. 1 is paramagnetic with μeff of one unpaired electron (1.63 μB and displays an axial EPR spectrum in the solid state with <g> = 2.07, characteristic of a (dx2−y2)1 ground state (g|| > g⊥; A|| = 16 mT). In cyclic voltammetry, 1 displays a two-electron oxidation around 0.9 V versus NHE. The two-electron oxidized (coulometrically) solution of 1 (golden yellow) gives an EPR spectrum with <g> = 2.17 and g|| < g⊥. The reaction of PPh3 with 1 yields the orange complex [Cu(LH2)(PPh3)](ClO4)2 (4). With the assumed chemical formula, the effective magnetization of 4 corresponds to one electron. Its EPR spectrum in the solid state is isotropic with g = 2.07. This g value yields a theoretical μeff of 1.80 μB at 298 K from Curie’s law, which matches very well with the experimental value of 1.89 μB at room temperature. Since single crystals of 4 could not be obtained, DFT calculations at the UBP86/6–311G(2d,p) level have been carried out and indicate that the cation in 4 is square pyramidal with the phosphine at the apex. The ease of the oxidation of the metal in 1 leads to the stabilization of the rare Cu(II)-P bond in 4.