Substituent’s Effects of PNP Ligands in Ru(II)-Catalyzed CO2 Hydrogenation to Formate: Theoretical Analysis Considering Steric Hindrance and Promotion of Hydrogen Bonding

This paper investigates the effects of substituents in PNP-type ruthenium complexes in the catalytic hydrogenation of CO2 to formate using the DFT method. Six groups were considered as substituents linked to the P atom of the PNP ligand: hydrogen, methyl, iso-propyl, tert-butyl, cyclopentyl, and cyclohexyl. The substituent effects were analyzed from the perspectives of steric hindrance and promotion of hydrogen bonding. With the joint functions of steric hindrance and hydrogen bonding promotion during the CO2 coordination step, hydride addition step, and HCOO− rotation step, these groups exhibited very different substituent effects. The results showed that the methyl group was the most favorable substituent when the solvent’s effects were not included, as it formed hydrogen bonding with relatively weak steric hindrance. The second favorable substituent was the iso-propyl group, while the tert-butyl group was the most unfavorable one, due to remarkable steric hindrance. When the substituent was cyclopentyl or cyclohexyl, the complex provided a wider open space for the reaction compared with the tert-butyl-substituted complex, because cyclopentyl and cyclohexyl are cyclic groups. Therefore, the principle for choosing the substituent in PNP-type complexes allowing the design of highly efficient catalysts for CO2 hydrogenation indicates that more hydrogen atoms but wider open space are ideal. In addition, the substituent’s effects can be markedly impacted by the solvent used.