A theoretical study on the hydrogenation of CO₂ to methanol catalyzed by ruthenium pincer complexes

Herein, a density functional theory (DFT) study was performed to investigate thoroughly the cascade reaction mechanism for the hydrogenation of carbon dioxide to methanol catalyzed by ruthenium pincer complex [RuH₂(Me₂PCH₂SiMe₂)₂NH(CO)]. Three catalytic stages involving the hydrogenation of carbon dioxide (stage I), formic acid (stage II) and formaldehyde (stage III) were studied. The calculated results show that the dominant H₂ activation strategy in the hydrogenation of CO₂ to methanol may not be the methanol-assisted H₂ activation, but the formate-assisted H₂ activation. In this cascade reaction, all energy spans of stage I, II and III are 20.2 kcal mol^-1 of the formate-assisted H₂ activation. This implies that it could occur under mild conditions. Meanwhile, the catalyst is proposed to be efficient for the transfer hydrogenation using isopropanol as the hydrogen resource, and the ruthenium pincer complexes [RuH₂(Me₂PCH₂SiMe₂)₂NH(CO)], [RuH₂(Ph₂PCH₂SiMe₂)₂NH(CO)] and [RuH₂(Me₂PCH₂SiMe₂)₂NH(CO)] exhibit similar catalytic activities for the hydrogenation of CO₂ to methanol.