The [{Ir (μ-Cl)(CO) 2} 2](I)-catalyzed reaction of terminal alkynes and diynes with Me3SiI with the aid of NEt (i-Pr) 2 occurs smoothly, leading to the formation of mono-and bis-silyl- functionalized alkynyl derivatives. This new reaction, which occurs via direct activation of the Csp− H bond in the starting alkyne, is a very efficient and easy tool for the synthesis of unique silylated alkynes. Separate experiments of the equimolar reactions of the ...