Primary alkynes R′CCH [R′=Me 3 Si, Tol, CH 2 OH, CO 2 Me, (CH 2 ) 4 CCH, Me] insert into the metal–carbon bond of diruthenium μ-aminocarbynes [Ru 2 {μ-CN(Me)(R)}(μ-CO)(CO)(MeCN)(Cp) 2 ][SO 3 CF 3 ] [R=2,6-Me 2 C 6 H 3 (Xyl), 1a; CH 2 Ph (Bz), 1b; Me, 1c] to give the vinyliminium complexes [Ru 2 {μ-η 1 :η 3 -C(R′)CHCN(Me)(R)}(μ-CO)(CO)(Cp) 2 ][SO 3 CF 3 ] [R=Xyl, R′=Me 3 Si, 2a; R=Bz, R′=Me 3 Si, 2b; R=Me, R′=Me 3 Si, 2c; R=Xyl, R′=Tol, 3a; R=Bz, R′=Tol, 3b; R=Bz, R′=CH 2 OH, 4; R=Bz, R′=CO 2 Me, 5a; R=Me, R′=CO 2 Me, 5b; R=Xyl, R′=(CH 2 ) 4 CCH, 6; R=Xyl, R′=Me, 7a; R=Bz, R′=Me, 7b; R=Me, R′=Me, 7c]. The related compound [Ru 2 {μ-η 1 :η 3 -C[C(Me)CH 2 ]CHCN(Me)(Xyl)}(μ-CO)(CO)(Cp) 2 ][SO 3 CF 3 ], (9) is better prepared by reacting [Ru 2 {μ-CN(Me)(Xyl)}(μ-CO)(CO)(Cl)(Cp) 2 ] (8) with AgSO 3 CF 3 in the presence of HCCC(Me)CH 2 in CH 2 Cl 2 at low temperature.In a similar way, also secondary alkynes can be inserted to give the new complexes [Ru 2 {μ-η 1 :η 3 -C(R′)C(R′)CN(Me)(R)}(μ-CO)(CO)(Cp) 2 ][SO 3 CF 3 ] (R=Bz, R′=CO 2 Me, 11; R=Xyl, R′=Et, 12a; R=Bz, R′=Et, 12b; R=Xyl, R′=Me, 13). The reactions of 2–7, 9, 11–13 with hydrides (i.e., NaBH 4 , NaH) have been also studied, affording μ-vinylalkylidene complexes [Ru 2 {μ-η 1 :η 3 -C(R′)C(R″)C(H)N(Me)(R)}(μ-CO)(CO)(Cp) 2 ] (R=Bz, R′=Me 3 Si, R″=H, 14a; R=Me, R′=Me 3 Si, R″=H, 14b; R=Bz, R′=Tol, R″=H, 15; R=Bz, R′=R″=Et, 16), bis-alkylidene complexes [Ru 2 {μ-η 1 :η 2 -C(R′)C(H)(R″)CN(Me)(Xyl)}(μ-CO)(CO)(Cp) 2 ] (R′=Me 3 Si, R″=H, 17; R′=R″=Et, 18), acetylide compounds [Ru 2 {μ-CN(Me)(R)}(μ-CO)(CO)(CCR′)(Cp) 2 ] (R=Xyl, R′=Tol, 19; R=Bz, R′=Me 3 Si, 20; R=Xyl, R′=Me, 21) or the tetranuclear species [Ru 2 {μ-η 1 :η 2 -C(Me)CCN(Me)(Bz)}(μ-CO)(CO)(Cp) 2 ] 2 (23) depending on the properties of the hydride and the substituents on the complex. Chromatography of 21 on alumina results in its conversion into [Ru 2 {μ-η 3 :η 1 -C[N(Me)(Xyl)]C(H)CCH 2 }(μ-CO)(CO)(Cp) 2 ] (22). The crystal structures of 2a[CF 3 SO 3 ]·0.5CH 2 Cl 2 , 12a[CF 3 SO 3 ] and 22 have been determined by X-ray diffraction studies.