Dinuclear Nickel Complexes of Thiolate-Functionalized Carbene Ligands and Their Electrochemical Properties

Four dimeric nickel(II) complexes [Ni₂Cl₂(BnC₂S)₂] [1], [Ni₂Cl₂(BnC₃S)₂] [2], [Ni₂(PyC₂S)₂]Br₂ [3]Br₂, and [Ni₂(PyC₃S)₂]Br₂ [4]Br₂ of four different thiolate-functionalized N-heterocyclic carbene (NHC) ligands were synthesized, and their structures have been determined by single-crystal X-ray crystallography. The four ligands differ by the alkyl chain length between the thiolate group and the benzimidazole nitrogen (two -C₂- or three -C₃- carbon atoms) and the second functionality at the NHC being a benzyl (Bn) or a pyridylmethyl (Py) group. The nickel(II) ions are coordinated to the NHC carbon atom and the pendent thiolate group, which bridges to the second nickel(II) ion creating the dinuclear structure. Additionally, in compounds [1] and [2], the fourth coordination position of the square-planar Ni(II) centers is occupied by the halide ions, whereas in [3]²⁺ and [4]²⁺, the additional pendant pyridylmethyl groups complete the coordination spheres of the nickel ions. The electrochemical properties of the four complexes were studied using cyclic voltammetry and controlled-potential coulometry methods. The thiolate-functionalized carbene complexes [1] and [2] appear to be poor electrocatalysts for the hydrogen evolution reaction; the complexes [3]Br₂ and [4]Br₂, bearing an extra pyridylmethyl group, show higher catalytic activity in proton reduction, indicating that the pyridine group plays an important role in the catalytic cycle.