The reaction behaviour of the bis(alkynyl) titanocenes [Ti](CCR 1)(CCR 2) {[Ti]=(η 5-C 5H 4SiMe 3) 2Ti; 1: R 1=R 2=Fc, Fc=(η 5-C 5H 4)Fe(η 5-C 5H 5); 5a: R 1=R 2=SiMe 3; 5b: R 1=R 2=C 6H 5; 5c: R 1=SiMe 3, R 2=C 6H 5} towards MX 2 (M=Pd, Pt; X=Cl; M=Cu; X=Cl, Br, OAc, acac) and MCl 3 (M=Fe, Au) is described. All reactions are dominated by redox processes. Generally, the reaction of 1 or 5a– 5c with AuCl 3 or MCl 2 (M=Cu, Pd, Pt) produces the titanocene dichloride [Ti]Cl 2 ( 3a) along with the corresponding butadiynes R 1CCCCR 2 ( 4: R 1=R 2=Fc; 7a: R 1=R 2=SiMe 3; 7b: R 1=R 2=C 6H 5; 7c: R 1=SiMe 3, R 2=C 6H 5) and M(0) (M=Cu, Au, Pd, Pt). As key intermediates the heterobimetallic tweezer complexes {[Ti](CCR 1)(CCR 2)}MCl 2 (M=Cu, Pd, Pt) are formed. These reactions are strongly solvent dependent. While {[Ti](CCFc) 2}CuCl 2 ( 2) is readily formed as the main product when 1 is reacted with CuCl 2 in diethyl ether, it is found that 2 affords 3a, 4 and Cu(0) on prolonged stirring in tetrahydrofuran. In contrast, complexes 5a– 5c produce with equimolar amounts of CuX 2 (X=Cl, Br) the compounds [Ti]X 2 ( 3a: X=Cl, 3b: X=Br), R 1CCCCR 2 ( 7a: R 1=R 2=SiMe 3; 7b: R 1=R 2=C 6H 5; 7c: R 1=SiMe 3, R 2=C 6H 5), {[Ti](CCR 1)(CCR 2)}CuX ( 6a: R 1=R 2=SiMe 3, X=Cl; 6b: R 1=R 2=SiMe 3, X=Br; 6c: R 1=R 2=C 6H 5, X=Cl; 6d: R 1=SiMe 3; R 2=C 6H 5, X=Cl) as well as 1/ n[CuX] n (X=Cl, Br). However, when 5a is treated with Cu(OAc) 2 or Cu(acac) 2 in a 1:1 ratio, heterobimetallic {[Ti](CCSiMe 3) 2}CuX ( 6e: X=OAc, 6f: X=acac) is the only isolated species. Possible mechanisms for the reactions presented are described.