The reaction of [Ti](CCPh) 2 ( 1) {[Ti]=(η 5-C 5H 4SiMe 3) 2Ti} with equimolar amounts of CuBr, Ni(PPh 3) 3 or Pd(PPh 3) 4 produces the heterobimetallic early–late transition metal complexes of general type {[Ti](CCPh) 2}MX [ 2: MX=CuBr, 3: MX=Ni(PPh 3), 4: MX=Pd(PPh 3)} in which the respective transition metal atoms are linked by σ,π-bound alkynyl ligands. The solid-state structure of 1 and 4 is reported. In heterobimetallic 4 the Pd(0) centre possesses a trigonal–planar environment caused by the two η 2-coordinated Me 3SiCC ligands and the datively bonded PPh 3 group. The PPh 3 moiety is thereby located out of the best Ti(CCSi) 2Pd plane. Comparative cyclic voltammetric studies on complexes 1– 4 as well as {[Ti](CCPh) 2}Ni(CO), for comparison, are presented. These studies reveal a strong influence of the η 2-coordinated low-valent transition metal complex fragments MX on the reduction behaviour of the Ti(IV) centre.