Nickel Pyridinethiolate Complexes as Catalysts for the Light-Driven Production of Hydrogen from Aqueous Solutions in Noble-Metal-Free Systems

A series of mononuclear nickel­(II) thiolate complexes (Et4N)­Ni­(X-pyS)3 (Et4N = tetraethylammonium; X = 5-H (1a), 5-Cl (1b), 5-CF3 (1c), 6-CH3 (1d); pyS = pyridine-2-thiolate), Ni­(pySH)4(NO3)2 (2), (Et4N)­Ni­(4,6-Y2-pymS)3 (Y = H (3a), CH3 (3b); pymS = pyrimidine-2-thiolate), and Ni­(4,4′-Z-2,2′-bpy)­(pyS)2 (Z = H (4a), CH3 (4b), OCH3 (4c); bpy = bipyridine) have been synthesized in high yield and characterized. X-ray diffraction studies show that 2 is square planar, while the other complexes possess tris-chelated distorted-octahedral geometries. All of the complexes are active catalysts for both the photocatalytic and electrocatalytic production of hydrogen in 1/1 EtOH/H2O. When coupled with fluorescein (Fl) as the photosensitizer (PS) and triethylamine (TEA) as the sacrificial electron donor, these complexes exhibit activity for light-driven hydrogen generation that correlates with ligand electron donor ability. Complex 4c achieves over 7300 turnovers of H2 in 30 h, which is among the highest reported for a molecular noble metal-free system. The initial photochemical step is reductive quenching of Fl* by TEA because of the latter’s greater concentration. When system concentrations are modified so that oxidative quenching of Fl* by catalyst becomes more dominant, system durability increases, with a system lifetime of over 60 h. System variations and cyclic voltammetry experiments are consistent with a CECE mechanism that is common to electrocatalytic and photocatalytic hydrogen production. This mechanism involves initial protonation of the catalyst followed by reduction and then additional protonation and reduction steps to give a key Ni–H/N–H+ intermediate that forms the H–H bond in the turnover-limiting step of the catalytic cycle. A key to the activity of these catalysts is the reversible dechelation and protonation of the pyridine N atoms, which enable an internal heterocoupling of a metal hydride and an N-bound proton to produce H2.