赵义,刘玉霞,毕思玮,刘永军^*.Theoretical study on copper-cataly zed reaction of hydrosilane,alkyne and carbon dioxide: A hydrocarboxylation or a hydrosilylation process ? Journal of Organometallic Chemistry,2013,745:166-172.F=2.0 　　  

　　Abstract:The hydrocarboxylation and hydrosilylation processes proposed in the copper-catalyzed reaction among carbon dioxide, diphenylacetylene and HSi(OEt)3 were comparatively studied with the aid of density functional theory calculations.Our study is to explorewhy the reactionpreferred a hydrocarboxylation rather than a hydrosilylation process. It was found that the s bond metathesis between CueC and HeSi involved in the hydrosilylationprocess had a significantly high reaction barrier in the presence of CO₂ (47.4 kcal/mol). Instead,CO₂ insertion and the subsequent s bond metathesis between CueO and HeSi involved in the hydrocarboxylation process were confirmed kinetically feasible, consistent with the experimental facts.