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[Cp*RuCl] 4 catalyzes the addition of i Pr 3 SiC≡CX (X = H, Cl) across internal alkynes with formation of 1,3-enyne or 1-chloro-1,3-enyne derivatives, respectively; the reaction follows an unorthodox trans -addition mode. The well-balanced affinities of the different reaction partners to the ruthenium catalyst ensure that crossed addition prevails over homodimerization of the individual components, as can be deduced from spectroscopic and crystallographic data of various intermediates; this includes a dinuclear complex in which an internal alkyne bridges two [Cp*RuCl] fragments.

Ruthenium-Catalyzed trans-Hydroalkynylation and trans-Chloroalkynylation of Internal Alkynes