Theoretical study on copper-catalyzed reaction of hydrosilane, alkyneand carbon dioxide: A hydrocarboxylation or a hydrosilylation process ?

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 theorycalculations. Our study is to explorewhy the reactionpreferred ahydrocarboxylation 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 presenceof 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. 2013 Elsevier B.V. All rights reserved.