H2 Evolution from a Thiolate-Bound Ni(III) Hydride

Terminal NiIII hydrides are proposed intermediates in proton reduction catalyzed by both molecular electrocatalysts and metalloenzymes, but well-defined examples of paramagnetic nickel hydride complexes are largely limited to bridging hydrides. Herein, we report the synthesis of an S = 1/2, terminally bound thiolate–NiIII–H complex. This species and its terminal hydride ligand in particular have been thoroughly characterized by vibrational and EPR techniques, including pulse EPR studies. Corresponding DFT calculations suggest appreciable spin leakage onto the thiolate ligand. The hyperfine coupling to the terminal hydride ligand of the thiolate–NiIII–H species is comparable to that of the hydride ligand proposed for the Ni–C hydrogenase intermediate (NiIII–H–FeII). Upon warming, the featured thiolate–NiIII–H species undergoes bimolecular reductive elimination of H2. Associated kinetic studies are discussed and compared with a structurally related FeIII–H species that has also recently been reported to undergo bimolecular H–H coupling.