The potential in preparative chemistry of the precursors trans-[Ru(NH 3 ) (C≡C-R 1 ) (Ph 2 PCH 2 CH 2 PPh 2 ) 2 ]PF 6 (3) has been studied. They offer a convenient access, by NH 3 displacement, to new functional alkynyl-ruthenium derivatives. Complexes 3 react with alkynes HC≡C-R 2 to give unsymmetrical trans-Ru(-C≡C-R 1 ) (-C≡C-R 2 ) (dppe) 2 compounds 4a-c, and with sodium methoxide in methanol they open the route to a variety of mixed hydride complexes 5a-c, trans-Ru(H) (-C≡C-R 1 ) (dppe) 2 . In contrast, with carbon monoxide or isocyanides C≡N-R 3 (R 3 : CH 2 Ph, C 6 H 1 1 , Me 3 C) they allow the preparation of cationic derivatives trans-(Ru(CO) (-C≡-R 1 ) (dppe) 2 ]PF 6 (6a-c) or trans-[Ru(CNR 3 ) (-C≡C-R 1 ) (dppe) 2 ]PF 6 (7a-d).