The Guerbet reaction is important for the synthesis of longer-chain monoalcohols like isobutanol through catalytic transfer hydrogenation from short-chain methanol and ethanol. However, the mechanism becomes complicated, especially considering the variations in the different metal-ligand cooperation (MLC) catalysts used. In order to further understand the Guerbet reaction, DFT studies were performed to figure out the detailed mechanism initiated by the unique Mn-PCP MLC Catalyst. Our results suggest that even with the assistance of the carbanion site of the PCP ligand, the direct substitution mechanism is less favored than the condensation-reduction mechanism. The key step of the reaction is the final reduction of the carbonyl, in which the 1,4-reduction of the unsaturated aldehyde is prior to the 3,4-reduction or 1,2-reduction due to the stronger interaction between the catalyst and the substrate. It is found that the production of isobutanol is preferred over n-butanol because of the lower total free energy barrier and lower relative free energy of the product. Finally, by changing the electronic effect of the carbanion site of the catalyst, we found that the relation between the electronic effect and the highest free energy span was not monotonous and a point with optimal electronic effect exists numerically.
Keywords: Alcohol, Aldol zondensation; Maganese; Subsititution; metal-ligand cooperation.
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