Redox and Acid-Base Properties of Binuclear 4-Terphenyldithiophenolate Complexes of Nickel

Abstract

This work reports on the redox and acid-base properties of binuclear complexes of nickel from 1,4-terphenyldithiophenol ligands. The results provide insight into the cooperative electronic interaction between a dinickel core and its ligand. Donor/acceptor contributions flexibly adjust to stabilize different redox states at the metals, which is relevant for redox reactions like proton reduction. Proton transfer to the [S2 Ni2 ] core and Ni-H bond formation are kinetically favored over the thermodynamically favored yet unproductive proton transfer to ligand.

Keywords: binuclear complexes; ligand cooperativity; nickel; proton reduction; thiophenolato ligands.