In this study, we report a pair of electrocatalysts for the hydrogen evolution reaction (HER) based on the noninnocent ligand diacetyl-2-(4-methyl-3-thiosemicarbazone)-3-(2-pyridinehydrazone) (H₂DMTH, H₂L¹). The neutral complexes NiL¹ and PdL¹ were synthesized and characterized by spectroscopic and electrochemical methods. The complexes contain a non-coordinating, basic hydrazino nitrogen that is protonated during the HER. The pK_a of this nitrogen was determined by spectrophotometric titration in acetonitrile to be 12.71 for NiL¹ and 13.03 for PdL¹. Cyclic voltammograms of both NiL¹ and PdL¹ in acetonitrile exhibit diffusion-controlled, reversible ligand-centered events at -1.83 and -1.79 V (vs ferrocenium/ferrocene) for NiL¹ and PdL¹, respectively. A quasi-reversible, ligand-centered event is observed at -2.43 and -2.34 V for NiL¹ and PdL¹, respectively. The HER activity in acetonitrile was evaluated using a series of neutral and cationic acids for each catalyst. Kinetic isotope effect (KIE) studies suggest that the precatalytic event observed is associated with a proton-coupled electron transfer step. The highest turnover frequency values observed were 6150 s^-1 at an overpotential of 0.74 V for NiL¹ and 8280 s^-1 at an overpotential of 0.44 V for PdL¹. Density functional theory (DFT) computations suggest both complexes follow a ligand-centered HER mechanism where the metals remain in the +2 oxidation state.

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