The reaction of [Cp*TaCl 4 ] (1a, Cp* ϭ C 5 Me 5 ) or [CpЈTaCl 4 (THF)] (1b, CpЈ ϭ C 5 MeH 4 ) with PH 2 Fc [Fc ϭ Fe(η 5 -C 5 H 5 )(η 5 -C 5 H 4 )] and PH 2 CH 2 Fc gives the primary ferrocenylphosphine complexes [Cp R TaCl 4 (PH 2 Fc)] [Cp R ϭ Cp* (2a), CpЈ (2b)] and [Cp R TaCl 4 (PH 2 CH 2 Fc)] [Cp R ϭ Cp* (3a), CpЈ (3b)], respectively. 1 reacts with (PH 2 ) 2 fc [fc ϭ Fe(η 5 -C 5 H 4 ) 2 ] or with the new secondary phosphine PH(CH 2 Fc) 2 to give the ferrocenyl-bridged complexes [{(Cp R TaCl Complexes 1b and 2Ϫ5 were characterised spectroscopically ( 1 H, 13 C, 31 P NMR, MS, IR ) and 1b, 2a, 3a, 4a, and 5a also by X-ray crystallography. The electrochemical behaviour of complexes 3a and 5b exhibits complicated electron transfer processes, which are due to the complex redox activity of the corresponding ferrocenylphosphine ligands PH 2 CH 2 Fc and PH(CH 2 Fc) 2 .