The trifluorovinyl phosphine complexes [Cp*RhCl 2 {PR 3−x (CFCF 2 ) x }] (1 x=1, a R=Ph, b Pr i , c Et; 2 x=2, R=Ph) have been prepared by treatment of [Cp*RhCl(μ-Cl)] 2 with the relevant phosphine. The salt [Cp*RhCl(CNBu t ){PPh 2 (CFCF 2 )}]BF 4 , 3, was prepared by addition of Bu t NC to 1a in the presence of NaBF 4 . The salt [Cp*RhCl{κP,κS-(CF 2 CF)PPh(C 6 H 4 SMe-2)}]BF 4 was prepared as a mixture of cis (5a) and trans (5b) isomers by treatment of [Cp*RhCl(μ-Cl)] 2 with the phosphine-thioether (CF 2 CF)PPh(C 6 H 4 SMe-2), 4, in the presence of NaBF 4 . The structures of 1a–c and 5a have been determined by single-crystal X-ray diffraction. Intramolecular dehydrofluorinative carbon–carbon coupling between pentamethylcyclopentadienyl and trifluorovinylphosphine ligands of 1a, 3 and 5 has been attempted. No reaction was observed on treatment of the neutral complex [Cp*RhCl 2 {PPh 2 (CFCF 2 )}], 1a, with proton sponge, however, 5a underwent dehydrofluorinative coupling to yield [{η 5 ,κP,κS-(C 5 Me 4 CH 2 CFCF)PPh(C 6 H 4 SMe-2)}RhCl]BF 4 , 6. Other reactions, in particular addition of HF across the vinyl bonds of 5, occurred leading to a mixture of products. The cation of 3 underwent similar reactions.