Mononuclear Ni(III) complexes [NiIII(L)(P(C6H3-3-SiMe3-2-S)3)]0/1- (L = thiolate, selenolate, CH2CN, Cl, PPh3): relevance to the nickel site of [NiFe] hydrogenases.

The stable mononuclear Ni(III)-thiolate complexes [NiIII(L)(P(C6H3-3-SiMe3-2-S)3)]- (L = SePh (2), Cl (3), SEt (4), 2-S-C4H3S (5), CH2CN (7)) were isolated and characterized by UV-vis, EPR, IR, SQUID, CV, 1H NMR, and single-crystal X-ray diffraction. The increased basicity (electronic density) of the nickel center of complexes [NiIII(L)(P(C6H3-3-SiMe3-2-S)3)]- modulated by the monodentate ligand L and the substituted groups of the phenylthiolate rings promotes the stability and reactivity. In contrast to the irreversible reduction at -1.17 V (vs Cp2Fe/Cp2Fe+) for complex 3, the cyclic voltammograms of complexes [NiIII(SePh)(P(o-C6H4S)3)]-, 2, 4, and 7 display reversible NiIII/II redox processes with E(1/2) = -1.20, -1.26, -1.32, and -1.34 V (vs Cp2Fe/Cp2Fe+), respectively. Compared to complex 2 containing a phenylselenolate-coordinated ligand, complex 4 with a stronger electron-donating ethylthiolate coordinated to the Ni(III) promotes dechlorination of CH2Cl2 to yield complex 3 (kobs = (6.01 +/- 0.03) x 10-4 s-1 for conversion of complex 4 into 3 vs kobs = (4.78 +/- 0.02) x 10-5 s-1 for conversion of complex 2 into 3). Interestingly, addition of CH3CN into complex 3 in the presence of sodium hydride yielded the stable Ni(III)-cyanomethanide complex 7 with a NiIII-CH2CN bond distance of 2.037(3) A. The NiIII-SEt bond length of 2.273(1) A in complex 4 is at the upper end of the 2.12-2.28 A range for the NiIII-S bond lengths of the oxidized-form [NiFe] hydrogenases. In contrast to the inertness of complexes 3 and 7 under CO atmosphere, carbon monoxide triggers the reductive elimination of the monodentate chalcogenolate ligand of complexes 2, 4, and 5 to produce the trigonal bipyramidal complex [NiII(CO)(P(C6H3-3-SiMe3-2-S)3]- (6).