Density functional theory prediction of cobalt pincer complexes for catalytic dehydrogenation of ethanol

<p>A density functional theory (DFT) study reveals that dehydrogenation of ethanol catalyzed by aliphatic PNP pincer cobalt complexes, [(PNP^Et)Co(H)(OMe)] (<b>1a</b>) and [(PNP^Et)Co(H)(CH₂SiMe₃)] (<b>1b</b>) (PNP^Et = bis(2-(diethylphosphino)ethyl)amine), undergoes a self-promoted mechanism, in which an ethanol assists the formation of H₂ as a bridge for proton transfer. The calculated total free energy barriers of ethanol dehydrogenation catalyzed by <b>1a</b> and <b>1b</b> are 23.9 and 22.2 kcal mol⁻¹, respectively, which indicate that <b>1b</b> is a promising catalyst for the dehydrogenation of ethanol under mild conditions.