Abstract The selective synthesis of functional alkynylsilanes RC≡ C–(SiMe 2) m–X (m= 1, 3) was investigated. Monofunctionalization with or without protecting groups gave moderate to good yields of alkynyldimethylmonosilanes RC≡ CMe 2 SiX [R= Ph, X= Cl (1), NEt 2 (2), OMe (3), H (4), Br (5), I (6), Cp (8), C 5 H 4 Li (10), Ph (11); R= Pr, X= Ph (12)]. Compounds 4 and 8 were converted into the (alkyne) transition-metal complexes 4· Cp 2 Mo 2 (CO) 4 ( ...