New heteroleptic [Ni(ii) 1,1-dithiolate-phosphine] complexes: synthesis, characterization and electrocatalytic oxygen evolution studies.

Four new heteroleptic Ni(ii) complexes with general formula [Ni(ii)(LL')] (L = 2-(methylene-1,1'-dithiolato)-5-phenylcyclohexane-1,3-dione (L1) and 2-(methylene-1,1'-dithiolato)-5,5'-dimethylcyclohexane-1,3-dione (L2); L' = 1,2-bis(diphenylphosphino)ethane (dppe) and bis(diphenylphosphino)monosulphide methane (dppms) have been synthesized and characterized by elemental analysis and spectroscopy (IR, UV-Vis, 1H, 13C{1H} and 31P{1H} NMR). All complexes 1-4 have also been characterized by PXRD and single crystal X-ray crystallography. The solid state molecular structures revealed distorted square planar geometry about the four-coordinate Ni(ii) metal centre together with rare NiH-C intra/intermolecular anagostic interactions in axial positions. In these complexes supramolecular structures have been sustained by non-covalent C-HO, C-OH-O, C-Hπ, C-Hπ (NiCS2, chelate), ππ and HH interactions. Their electrocatalytic properties have been investigated for oxygen evolution reaction (OER) in which complex 2 showed the highest activity with 10 mA cm-2 at the potential of 1.58 V vs. RHE. In addition, complex 2 also exhibits an OER onset potential at 1.52 V vs. RHE.