Combined Experimental–Theoretical Characterization of the Hydrido-Cobaloxime [HCo(dmgH)2(PnBu3)]

• DOI: 10.1021/ic2024204
• Publication Date: 2012-06-19T14:59:24Z
• Authors: Anirban Bhattacha...; Murielle Chavarot...; Eugen. S. Andreiadis; Marc Fontecave; Martin J. Field; Vincent Artero
• Keywords: Characterization

A combined theoretical and experimental approach has been employed to characterize the hydrido-cobaloxime [HCo(dmgH)(2)(PnBu(3))] compound. This complex was originally investigated by Schrauzer et al. [Schrauzer al., J. Am. Chem. Soc. 1971, 93,1505] since referred as a key, stable analogue of hydride intermediate involved in hydrogen evolution catalyzed cobaloxime compounds [Artero, V. Angew. Chem., Int. Ed. 2011, 50, 7238-7266]. We quantum chemical calculations, using density functional theory correlated RI-SCS-MP2 methods, structural electronic properties compound observed important differences between calculated (1)H NMR spectrum that reported original study Holland. To calibrate model, hydrido tetraamine cobalt(III) [HCo(tmen)(2)(OH(2))](2+) (tmen = 2,3-dimethyl-butane-2,3-diamine) [Rahman, A. F. M. Commun. 2003, 2748-2749] subjected similar analysis, and, this case, results agreed well with those obtained experimentally. As follow-up computational work, title synthesized recharacterized experimentally, together Co(I) derivative, giving were agreement predictions.