Computational mechanistic study of Ru-catalyzed CO2 reduction by pinacolborane revealing the σ-π coupling mechanism for CO2 decarbonylation.

Abstract

It has been reported that RuH2(η2-H2)2(PCy3)2 (1) could mediate CO2 reduction by pinacolborane (HBpin), affording pinBOBpin (7), pinBOCH3 (8), pinBOCHO (9), pinBOCH2OBpin (10), and an unprecedented C2 species pinBOCH2OCHO (11), which meanwhile is converted to the Ru complexes, including the transient 3 (RuH(κ2-O2CH)(CO)(PCy3)2) and 5 (RuH{(μ-H)2Bpin}(CO)(PCy3)2), and the persistent 4 (RuH(κ2-O2CH)(CO)2(PCy3)2) and 6 (RuH2(CO)2(PCy3)2). To gain an insight into the catalysis, a DFT study was carried out. The study identified the key active catalyst to be the hydride 13 (RuH2(CO)(PCy3)2) and characterized the mechanisms leading to the experimentally observed species (3-11). By investigating the experimental system, we learned a new mechanism called σ-π coupling for CO2 decarbonylation. Under this mechanism, CO2 and HBpin first co-coordinate to the Ru center of 13, then σ-π coupling takes place, forming a B-O bond between CO2 and HBpin, Ru-H and Ru-C bonds, and simultaneously breaking the H-Bpin bond, followed by -OBpin group migration to the Ru center, completing the CO2 decarbonylation. An interesting feature regarding the Ru catalysis was the involvement of η1-Hη1-H → η2-H2 and η1-Hη1-Bpin → η2-HBpin reductions, which facilitated the oxidative H-Bpin addition or the coordination mode change of CO2 from η1-O to η2-CO for CO2 activation or σ-π coupling. The facilitation effects could be attributed to the reductions enhancing the electron donations from the Ru center to the antibonding orbitals of the activating bonds.