The present study reports the evidence for the multiple carbon–carbon bond insertion into the metal–heteroatom bond via a five-coordinate metal complex. Detailed analysis of the model catalytic reaction of the carbon–sulfur (CS) bond formation unveiled the mechanism of metal-mediated alkyne insertion: a new pathway of CS bond formation without preliminary ligand dissociation was revealed based on experimental and theoretical investigations. According to this pathway alkyne insertion into the metal–sulfur bond led to the formation of intermediate metal complex capable of direct CS reductive elimination. In contrast, an intermediate metal complex formed through alkyne insertion through the traditional pathway involving preliminary ligand dissociation suffered from “improper” geometry configuration, which may block the whole catalytic cycle. A new catalytic system was developed to solve the problem of stereoselective SS bond addition to internal alkynes and a cost-efficient Ni-catalyzed synthetic procedure is reported to furnish formation of target vinyl sulfides with high yields (up to 99 %) and excellent Z/E selectivity (>99:1).
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