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.
Datta
Ayan
A
Theoretical Sciences Unit, Jawaharlal Nehru Center for Advanced Scientific Research, Jakkur P. O, Bangalore-560064, India.
John
Neena S
NS
Kulkarni
G U
GU
Pati
Swapan K
SK