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The hydrosilylation of terminal alkyne is the most straightforward and atom‐economy method to generate α‐vinylsilane. In the present paper, the acetylene and phenylacetylene hydrosilylation reactions were firstly studied by imposing external electric field (EEF) as a catalyst at the level of ωB97XD/TZVP. The results demonstrated that the oriented negative FY direction is the optimal direction, which...
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