Controlling O2 Reactivity in Synthetic Analogues of [NiFeS]- and [NiFeSe]-Hydrogenase Active Sites

Strategies for limiting, or reversing, the degradation of air-sensitive, base metal catalysts for the hydrogen evolution/oxidation reaction on contact with adventitious O2 are guided by nature′s design of hydrogenase active sites. The affinity of oxygen for sulfur and selenium, in [NiFeS]- and [NiFeSe]-H2ase, yields oxygenated chalcogens under aerobic conditions, and delays irreversible oxygen damage at the metals by maintaining the NiFe core structures. To identify the controlling features of S-site oxygen uptake, related Ni(μ-EPhX)­(μ-S′N2)Fe (E = S or Se, Fe = (η5-C5H5)­FeII(CO)) complexes were electronically tuned by the para-substituent on μ-EPhX (X = CF3, Cl, H, OMe, NMe2) and compared in aspects of communication between Ni and Fe. Both single and double O atom uptake at the chalcogens led to the conversion of the four-membered ring core, Ni(μ-EPhX)­(μ-S′N2)Fe, to a five-membered ring Ni–O–E–Fe–S′, where an O atom inserts between E and Ni. In the E = S, X = NMe2 case, the two-oxygen uptake complex was isolated and characterized as the sulfinato species with the second O of the O2SPh‑NMe2 unit pointing out of the five-membered Ni–O–S–Fe–S′ ring. Qualitative rates of reaction and ratios of oxygen-uptake products correlate with Hammett parameters of the X substituent on EPhX. Density functional theory computational results support the observed remote effects on the NiFe core reactivity; the more electron-rich sulfurs are more O2 responsive in the SPhX series; the selenium analogues were even more reactive with O2. Mass spectral analysis of the sulfinato products using a mixture of 18O2/16O2 suggests a concerted mechanism in O2 addition. Deoxygenation, by reduction or O atom abstraction reagents, occurs for the 1-O addition complexes, while the 2-O, sulfinato, analogues are inert. The abstraction of oxygen from the 1-O, sulfenato species, is related to oxygen repair in soluble, NAD+-reducing [NiFe]-H2ase (Horch, M.; Lauterbach, L.; et al. J. Am. Chem. Soc. 2015, 137, 2555–2564).