A series of related Ti σ-acetylides of the type {Ti}CCR ({Ti}=(η 5 -C 5 H 5 ) 2 Ti(CH 2 SiMe 3 ); 2: R=SiMe 3 ; 3: R=C 6 H 3 (CH 2 NMe 2 ) 2 -3,5; 4: R=C 6 H 2 I-4-(CH 2 NMe 2 ) 2 -3,5; 5: R=C 6 H 4 CN-4; 6: R=C 5 H 4 N-4; 7: R=Fc, Fc=(η 5 -C 5 H 4 )Fe(η 5 -C 5 H 5 ); 8: R=C 6 H 4 (CC{Ti})-4) have been prepared by reacting the corresponding lithium acetylides with {Ti}Cl (1). The X-ray crystal structure determination of {Ti}CCSiMe 3 (2) is reported. This compound exhibits a one-dimensional (1D) arrangement with respect to the Ti–CC unit. The reaction of 2 with [CuCl] n afforded 1 and [CuCCSiMe 3 ] n (10) and is proposed to occur via prior formation of the dimeric intermediate [(η 2 -{Ti}CCSiMe 3 ) 2 Cu 2 Cl 2 ]. The chemical oxidation of {Ti}CCFc, 7, with Ag[BF 4 ] yielded HCCFc and an undefined Ti species. Treatment of 5 or 6 with {Ru}NN{Ru} ({Ru}=mer,trans-[RuCl 2 (NN′N)]; NN′N=η 3 -C 5 H 3 N(CH 2 NMe 2 ) 2 -2,6) produced intensively coloured heterodinuclear compounds, such as [{Ti}CCC 5 H 4 N-4]{Ru} (16). In contrast, 5 and 6 react with cationic Pt compounds of the type [{Pt}·L][X] ({Pt}=[Pt(C 6 H 3 {CH 2 NMe 2 } 2 -2,6] + ; L=H 2 O, MeCN; X=BF 4 , OTf) to give product mixtures rather than defined compounds. Electrochemical studies on some of the bimetallic compounds show that the Ti(III)/Ti(IV) redox potential appears to be reversible and is shifted to a more negative value upon substitution of the Cl ligand in 1 by CCR (compounds 2–8). Whereas the nature of R in {Ti}CCR has an influence on the Ti(III)/Ti(IV) redox potential, the attachment of a second metal onto the π-conjugated system has only negligible effect on the electrochemical properties of the Ti centre.