Mononuclear nickel and copper complexes with indolecarboxamide ligands: Synthesis, properties and electrochemistry

Few nickel(II) and copper(II) complexes have been prepared with three new indolecarboxamide ligands (H4L3, H4L4 and H4L5) offering two N-amide and two N-indole donor sites to the metal center. The ligands carry electron-donating (-CH3); -H; and electron-withdrawing (-Cl) substituents on the phenylene backbone to evaluate their effect on the structure and redox properties of the metal complexes. One of the representative nickel complexes has been structurally characterized and reveals that the ligand create a distorted square-planar geometry around the metal center. The electrochemical results suggest that the Ni3+/2+ and Cu3+/2+ redox couple primarily depends on the tetra-anionic N-4 donors; however, the electronic substituents shift the redox potentials by 285 mV. The observed M3+/2+ redox potentials (0.007-0.30 V versus SCE) for these complexes are considerably on lower side due to strong sigma-donation from the tetra-deprotonated form of the indolecarboxamide ligands. Based on the redox investigations, the transient M3+ species were generated electrochemically and characterized by the absorption spectroscopy. (C) 2011 Elsevier B.V. All rights reserved.