Reactions between (C5H4R')(2)TiCl2 and 2 equiv of LiEC=CR generated a series of alkynethiolato and alkyneselenolato complexes of titanocene(IV), (C5H4R')(2)Ti(EC=CR)(2) in high yields (1, R = Ph, R' = H, E = S; 2, R = P-C6H4CH3, R' = H, E = S; 3, R = Bu-t, R' = H, E = S; 4, R = Ph, R' = Me, E = S; 5, R = Ph, R' = H, E = Se). Complex 1 reacted with 1/2 equiv of Ni(cod)(2) to give a linear Ti2Ni trimetallic complex, [Cp2Ti(mu-SC=CPh)(2)](2)Ni (6), in which the Ni atom links two Cp2Ti(SC=CPh)(2) units through interactions with thiolate sulfur bridges. Treatment of Cp*(2)m(mu-Cl)(2)Li(OEt2)(2) with 2 equiv of LiSC=CPh and TMEDA resulted in [Li(tmeda)(2)] [Cp*Sm-2(SC=CPh)(2)] (7). The structures of complexes 4, 5, 6, and 7 were determined by X-ray diffraction analysis.