Abstract
A novel and efficient strategy for Rh/Mn bimetal catalyzed hydroformylation of formaldehyde was developed. The synergistic effect between RhCl(CO)(PPh3)2 and Mn2(CO)10 improves the reaction efficiency (TOFGA up to 86.7 h−1vs. 47.8 h−1 by using RhCl(CO)(PPh3)2 alone) and reduces the dosage of rhodium greatly. 81% yield of glycolaldehyde can be obtained even the concentration of RhCl(CO)(PPh3)2 was low to 5 × 10−4 mol/L. Density functional theory (DFT) calculations revealed the hydrogenation process of acyl rhodium species is the rate-determining step. Introduction of Mn2(CO)10 favors forming a binuclear Rh/Mn complex which reduces the energy barrier of hydrogenation step, thus promoting the hydroformylation of formaldehyde.
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