Metal-Free Reduction of CO_2 with Hydroboranes: Two Efficient Pathways at Play for the Reduction of CO_2 to Methanol

摘要

Guanidines and amidines prove to be highly efficient metal-free catalysts for the reduction of CO_2 to methanol with hydroboranes such as 9-borabicyclo[3.3.1]nonane (9-BBN) and catecholborane (catBH). Nitrogen bases, such as 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 7-methyl-1,5,7- triazabicyclo[4.4.0]dec-5-ene (Me-TBD), and 1,8-diazabicycloundec- 7-ene (DBU), are active catalysts for this transformation and Me-TBD can catalyze the reduction of CO_2 to methoxyborane at room temperature with TONs and TOFs of up to 648 and 33 h~(-1) (25 ℃), respectively. Formate HCOOBR_2 and acetal H_2C(OBR_2)_2 derivatives have been identified as reaction intermediates in the reduction of CO_2 with R_2BH, and the first C-H-bond formation is rate determining. Experimental and computational investigations show that TBD and Me-TBD follow distinct mechanisms. The N-H bond of TBD is reactive toward dehydrocoupling with 9-BBN and affords a novel frustrated Lewis pair (FLP) that can activate a CO_2 molecule and form the stable adduct 2, which is the catalytically active species and can facilitate the hydride transfer from the boron to the carbon atoms. In contrast, Me-TBD promotes the reduction of CO_2 through the activation of the hydroborane reagent. Detailed DFT calculations have shown that the computed energy barriers for the two mechanisms are consistent with the experimental findings and account for the reactivity of the different boron reductants.