Ligand redox controlled amine dehydrogenation and imine hemilability in singlet diradical azo-aromatic Ni(<scp>ii</scp>) complexes: characterization of the electron transfer series of azo-imine complexes of Ni(<scp>ii</scp>)
Bappaditya Goswami, Manas Khatua, Ambika Devi, Shivali Hans, Robindo Chatterjee, Subhas Samanta
Abstract
lengths of ∼1.28 Å. In cyclic voltammetry, complex [3a]2+ showed four well-resolved reversible reductive waves at 0.5 V to -1.6 V in dichloromethane. The first two waves became irreversible when they were measured in acetonitrile solution. The electron transfer series of [3a]2+ was further characterized by spectro-electrochemistry, EPR, and DFT calculations. These showed that all the reductions were associated with the ligand. It was further probed by redox events in complexes [3b]2+ and [3c]2+. While the electron donor -OMe group on the phenyl ring of the azo moiety in [3b]2+ showed a prominent cathodic shift of the potentials, the -F substitution on the phenyl group on the imine side arm of [3c]2+ has almost no effect. It has to be noted here that the oxidation of [2] by two electrons returns it back to complex [3a]2+. Reduction of [3a]2+ by two electrons also resulted in complex [2], indicating reversible ligand redox-induced hemilability of the imine moiety between [3a]2+ and [2]. Moreover, characterization of the electron transfer series of [3a]2+ and [2] has shown superior redox non-innocent behaviour and coordination ability of the azo-pyridine moiety in nickel(II) complexes over the imino-pyridine moiety of the ligand.