Acceleration Effect of Bases on Mn Pincer Complex-Catalyzed CO2 Hydroboration

Herein, we report a comprehensive study of CO2 hydroboration catalyzed by Mn pincer complexes. The traditional metal-ligand cooperation (MLC) mechanism based on the H-Mn-N-Bpin pincer complex is not viable due to the competing abstraction of the Bpin group from the H-Mn-N-Bpin complex by (NaOBu)-Bu-t. Instead, we propose an ionic mechanism based on the H-Mn-N-Na species with a low energy span (22.5 kcal/mol) and unveil the acceleration effect of bases. The X groups in the HMn-N-X catalyst models are further modulated, and the steric hindrance and H -> B donor-acceptor interactions of the X group increase the energy barrier of the hydride transfer. The hydrogen bond and electrostatic interactions of the X group can accelerate the hydride transfer to HCOOBpin and HCHO molecules except for the nonpolar CO2 molecule. Based on these discoveries, we designed a pyridine-based Mn pincer catalyst system, which could achieve CO2 hydroboration in low-temperature and base-free conditions through a metal-ligand cooperation mechanism.