Ancillary ligand electro-activity effects towards phenyl acetylene homocoupling reaction by a nickel(ii) complex of a non-innocent O-amino phenol ligand: a mechanistic insight

Abstract

A new Ni(II) complex, was synthesized from the reaction of a non-innocent o-aminophenol ligand, and Ni(OAc)₂. The crystal structure of Ni^IIL₂^NIS (in which, IS stands for iminosemiquinone radical ligand with cyanide (shown by N in NIS) substituent on phenolate rings) exhibits the square planar environment of Ni(II). The complex has been crystalized in the monoclinic system and Ni(II) was surrounded by two oxygen and two nitrogen atoms of two ligands. Variable-temperature magnetic susceptibility measurement for crystalline samples of complex shows the effective magnetic moment per molecule (μ_eff) of near zero and the diamagnetic nature of the complex (S = 0) which emphasize that strong antiferromagnetic coupling prevailed between the two unpaired electrons of L^NIS ligands and Ni(II) high spin electrons. The complex is EPR silent which confirms the diamagnetic character of the Ni(II) complex. Electrochemical measurement (CV) indicates the redox-active character of ligand and metal. Ni^IIL₂^NIS complex proved to be effective for free metal- or base counterpart homocoupling of phenyl acetylene at room temperature. To the best of our knowledge, this is the first example of using Ni(II) complex without using any reducing agent due to the promotion ancillary effect of non-innocent o-aminophenol ligand which acts as an “electron reservoir” and can reversibly accept and donate electrons in the catalytic cycle. The theoretical calculation confirms the magnetostructure, electronic spectrum and confirmed the suggested mechanism of phenyl acetylene homocoupling with emphasis on the role of non-innocent ligand electro-activity and the effect of ligand substituent on the efficiency and stability of the complex.