Aromaticity in Stable Tiara Nickel Thiolates:  Computational and Structural Analysis

Quantum chemical calculations as well as crystallographic analyses show that the Ni(n) rings in the tiara Ni thiolates, [NiS2]n and [Ni(SR)2]n (n = 3-6), have highly symmetric polygonal structures. We find that such structural features primarily arise from the effective delocalization of the d-orbital electrons across the Ni(n) rings leading to bond length equalization and thereby aromaticity. We introduce the d-orbital aromaticity for the first time to explain the experimentally observed polygonal structures of these cyclic metal rings bridged by thiol linkages.