Homoleptic Ni(II) dithiocarbamate complexes as pre-catalysts for the electrocatalytic oxygen evolution reaction

Four new functionalized Ni(II) dithiocarbamate complexes of the formula [Ni(L)] (1-4) (L₁ = N-methylthiophene-N-3-pyridylmethyl dithiocarbamate, L₂ = N-methylthiophene-N-4-pyridylmethyl dithiocarbamate, L₃ = N-benzyl-N-3-pyridylmethyl dithiocarbamate, and L₄ = N-benzyl-N-4-pyridylmethyl dithiocarbamate) have been synthesized and characterized by IR, UV-vis, and ¹H and ¹³C{¹H} NMR spectroscopic techniques. The solid-state structure of complex 1 has also been determined by single crystal X-ray crystallography. Single crystal X-ray analysis revealed a monomeric centrosymmetric structure for complex 1 in which two dithiocarbamate ligands are bonded to the Ni(II) metal ion in a S^S chelating mode resulting in a square planar geometry around the nickel center. These complexes are immobilized on activated carbon cloth (CC) and their electrocatalytic performances for the oxygen evolution reaction (OER) have been investigated in aqueous alkaline solution. All the complexes act as pre-catalysts for the OER and undergo electrochemical anodic activation to form Ni(O)OH active catalysts. Spectroscopic and electrochemical characterization revealed the existence of the interface of molecular complex/Ni(O)OH, which acts as the real catalyst for the OER. The active catalyst obtained from complex 2 showed the best OER activity achieving 10 mA cm^-2 current density at an overpotential of 330 mV in 1.0 M aqueous KOH solution.