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Abstract

Sulfur-rich nickel metalloenzymes are capable of stabilizing Ni^I and Ni^III oxidation states in catalytically relevant species. In an effort to better understand the structural and electronic features that allow the stabilization of such species, we have investigated the electrochemical properties of two mononuclear N₂S₂ Ni^II complexes that differ in their sulfur environment. Complex 1 features aliphatic dithiolate coordination ([NiL], 1), and complex 2I is characterized by mixed thiolate/thioether coordination ([NiL^Me]I, 2I). The latter results from the methylation of a single sulfur of 1. The X-ray structure of 2I reveals a distorted square planar geometry around the Ni^II ion, similar to what was previously reported by us for 1. The electrochemical investigation of 1 and 2⁺ shows that the addition of a methyl group shifts the potentials of both redox Ni^II/Ni^I and Ni^III/Ni^II redox couples by about 0.7 and 0.6 V to more positive values. Through bulk electrolyses, only the mononuclear dithiolate [NiIL]⁻ (1^-) and the mixed thiolate/thioether [Ni^IIIL^Me]²⁺ (2²⁺) complexes were generated, and their electronic properties were investigated by UV−vis and EPR spectroscopy. For 1^- (Ni^I, d⁹ configuration) the EPR data are consistent with a d_x²-y² based singly occupied molecular orbitals (SOMOs). However, DFT calculations suggest that there is also pronounced radical character. This is consistent with the small g-anisotropy observed in the EPR experiments. The spin population (Mulliken analysis) analysis of 1^- reveals that the main contribution to the SOMO (64%) is due to the bipyridine unit. Time dependent density functional theory (TD-DFT) calculations attribute the most prominent features observed in the electronic absorption spectrum of 1^- to metal to ligand charge transfer (MLCT) transitions. Concerning 2²⁺, the EPR spectrum displays a rhombic signal with g_x = 2.236, g_y = 2.180, and g_z = 2.039 in CH₃CN. The g_iso value is larger than 2.0, which is consistent with metal based oxidation. The unpaired electron (Ni^III, d⁷ configuration) occupies a Ni-d_z² based molecular orbital, consistent with DFT calculations. Nitrogen hyperfine structure is observed as a triplet in the g_z component of the EPR spectrum with A_N = 51 MHz. This result indicates the coordination of a CH₃CN molecule in the axial position. DFT calculations confirm that the presence of a fifth ligand in the coordination sphere of the Ni ion is required for the metal-based oxidation process. Finally, we have shown that 1 exhibits catalytic reductive dehalogenation activity below potentials of −2.00 V versus Fc/Fc⁺ in CH₂Cl₂.