The synthesis and properties of heterobimetallic Ti–Cd complexes of type {[Ti](μ-η 1:η 2–C CR) 2}CdX 2 ([Ti] = Ti(η 5–C 5H 4SiMe 3) 2; R = SiMe 3: 3a, X = Cl; 3b, X = Br; 3c, X = I; R = Fc: 3d, X = Br; Fc = Fe(η 5–C 5H 4)(η 5–C 5H 5) is reported. These compounds were accessible by treatment of [Ti](C CR) 2 ( 1a, R = SiMe 3; 1b, R = Fc) with the cadmium salts CdX 2 ( 2a, X = Cl; 2b, X = Br; 2c, X = I) in a 1:1 M ratio in diethyl ether. Dissolving, for example, 3b in tetrahydrofuran afforded coordination polymer [Cd(μ-Br) 2(thf) 2] n ( 4) along with the tweezer molecule 1a. Treatment of 3b with two equiv of LiC CFc ( 5) gave {[Ti](μ-η 1:η 2–C CSiMe 3) 2}Cd(C CFc) 2 ( 6) which eliminated at ambient temperature the all-carbon buta-1,3-diyne FcC C–C CFc ( 7) producing 1a and elemental Cd. The same reaction behavior was observed, when 2b was reacted with 5. The thus obtained bis(alkynyl) cadmium complex Cd(C CFc) 2 ( 8) is redox-active at low temperature producing 7 and Cd(0). When mercury halides HgX 2 ( 9a, X = Cl; 9b, X = Br) are used, then the titanocene dihalides [Ti]X 2 ( 10a, X = Cl; 10b, X = Br) together with Me 3SiC C–C CSiMe 3 ( 11) and Hg(0) were formed. Nevertheless, mercury acetylides were available by treatment of Hg(OAc) 2 ( 12) with HC CFc ( 13) in a 1:2 M ratio. Thus obtained Hg(C CFc) 2 ( 14) gave with [CuBr] ( 15) coordination polymer [{Hg(η 2-C CFc) 2}(Cu 2(μ-Br) 2] n ( 16), while with [AgPF 6] oxidation of the ferrocenyl moieties took place affording dicationic [Hg(C CFc) 2] 2+ ( 18). The structures of 3b and 4 in the solid state are reported. Compound 3b shows the typical characteristics for heterobimetallic organometallic π-tweezer complexes with cadmium in a tetrahedral environment, while 4 corresponds to a one-dimensional coordination polymer in which the Cd(II) ions are linked in a edge-sharing fashion by bromide bridges in the pseudo-equatorial plane. The appropriate tetrahydrofuran molecules are completing the pseudo-octahedral coordination sphere at cadmium. The cyclic voltammogram of 14 is reported showing a single reversible redox event at E 0 = 0.108 V with Δ E p = 76 mV indicating that there is no communication between the Fc termini along the mercury acetylide unit.