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|Abstract:||The bis(arylimidazol-2-ylidene)pyridine cobalt methyl complex, ((CNC)-C-iPr)CoCH3, was evaluated for the catalytic hydrogenation of alkenes. At 22 degrees C and 4 atm of H-2 pressure, ((CNC)-C-iPr)CoCH3 is an effective precatalyst for the hydrogenation of sterically hindered, unactivated alkenes such as trans-methylstilbene, 1-methyl-1-cyclohexene, and 2,3-dimethyl-2-butene, representing one of the most active cobalt hydrogenation catalysts reported to date. Preparation of the cobalt hydride complex, ((CNC)-C-iPr)CoH, was accomplished by hydrogenation of ((CNC)-C-iPr)CoCH3. Over the course of 3 h at 22 degrees C, migration of the metal hydride to the 4-position of the pyridine ring yielded (4-H-2-(CNC)-C-iPr)CoN2. Similar alkyl migration was observed upon treatment of ((CNC)-C-iPr)CoH with 1,1-diphenylethylene. This reactivity raised the question as to whether this class of chelate is redox-active, engaging in radical chemistry with the cobalt center. A combination of structural, spectroscopic, and computational studies was conducted and provided definitive evidence for bis(arylimidazol-2-ylidene)pyridine radicals in reduced cobalt chemistry. Spin density calculations established that the radicals were localized on the pyridine ring, accounting for the observed reactivity, and suggest that a wide family of pyridine-based pincers may also be redox-active.|
|Citation:||Yu, Renyuan Pony, Darmon, Jonathan M, Milsmann, Carsten, Margulieux, Grant W, Stieber, S Chantal E, DeBeer, Serena, Chirik, Paul J. (2013). Catalytic Hydrogenation Activity and Electronic Structure Determination of Bis(arylimidazol-2-ylidene)pyridine Cobalt Alkyl and Hydride Complexes. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 135 (13168 - 13184. doi:10.1021/ja405608u|
|Pages:||13168 - 13184|
|Type of Material:||Journal Article|
|Journal/Proceeding Title:||JOURNAL OF THE AMERICAN CHEMICAL SOCIETY|
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