羰基钴催化烯烃醛化反应中RCOCo(H)_2(CO)_3还原消去关键步骤的理论研究

Theoretical Studies on the Reductive Elimination of RCOCo(H)2(CO), in the Hydroformylation of Olefins with Cobalt Carbonyl as Catalyst

在其催化循环过程中,RCOCo(CO)_3与H2_氧化加成生成RCOCO(H)_2(CO)_3,此中间体进一步还原消去生成醛是涉及氢在整个醛化反应催化循环中活化作用的关键步骤,文献[2]认为它是整个循环的控制步骤,由于反应的各中间物光谱无法准确测定。

The reductive elimination of RCOC6(H)2(CO)3, one of the key reaction in the hydro-formylation of olefins with cobalt carbonyl as a catalyst, has been studied in details by the semiemperi-cal method——ASED-MO. As a result, the reaction energy surfaces, reaction pathway, activation.energies and reaction heats have been obtained. On the basis, the authors have made a comparison between the results obtained here and others from previous paper on the key reaction of oxidative addition for hydrogen to species RCOCo(CO)3. The oxidative addition is a rate-determining step and the species RCOCo(H)2(CO)3 could be an unstable intermediate.