The synthesis and reaction chemistry of the mono (sigma-alkynyl) titanocene chlorides [Ti](CI)(C=CR) {[Ti] = (eta(5)-C(5)H(4)SiMe(3))(2)Ti; 2a, R = Ph; 2b, R = SiMe(3)} is described. Treatment of compounds 2a and 2b with ClMgCH(2)SiMe(3) or LiC=CR’ yields [Ti](CH(2)SiMe(3))(C=CSiMe(3)) (3) or [Ti](C=CR)(C=CR’) (5a, R = Ph, R’ = SiMe(3); 5b, R = R’ = Ph; 5c, R = R’ = SiMe(3)), respectively. The reaction of compounds 2a, 2b, or 5a with polymeric [CuX](n) (X = Cl, Pr, I) produces the heterobimetallic titanium-copper complexes {[Ti](Cl)(C=CR)}CuX-(6a, R = Ph, X = Cl; 6b, R = Ph, X = Br; 6c, R = Ph, X = I; 7a, R = SiMe(3), X = Ci; 7b, R = SiMe(3), X = Br) or {[Ti](C=CPh)(C=CSiMe(3))}CuX (8a, X = Cl; 8b, X = Pr). While compounds 2a and 2b do not react with [AgX](n) (X = Cl, Pr), it is found that the bis(sigma-alkynyl)titanocene 5a is able to break down the polymeric structure of [AgX](n) to produce the heterobimetallic compounds {[Ti](C=CPh)(C=CSiMe(3))}AgX (10a, X = Cl; 10b, X = Pr). Moreover, compound 8a can be synthesized by treatment of 2a or 2b with [CuC=CR’](n) (R’ = SiMe(3), Ph). However, when compound 3 is reacted with [CuCl](n) under appropriate reaction conditions, the formation of {[Ti](C=CSiMe(3))(2)})CuCl (sb), [CuCH(2)SiMe(3)](4), [Ti](Cl)(CH(2)SiMe(3)) (4), and [Ti]Cl-2 (1) is observed; a reaction mechanism for the formation of the latter compounds is discussed. The solid state structures of [Ti](Cl)(CH(2)SiMe(3)) (4) and {[Ti](Cl)(C=CSiMe(3))}CuBr (7b) were determined. Crystals of 4 and 7b are monoclinic, space group P2(1)/n. 4 : C20H37ClSi3Ti, cell constants a = 6.812(2) Angstrom, b = 11.298(6) Angstrom, c = 33.16(1) Angstrom, beta = 92.25(3)degrees, and Z = 4. 7b : C21H35BrClCuSi3Ti, cell constants a = 13.257(7) Angstrom, b = 10.470(5) Angstrom, c = 20.39(1) Angstrom, beta 100.91(3)degrees, and Z = 4.