The trifluoropropynyl ligand -C≡CCF(3) was studied as a possible surrogate for the cyano ligand. Complexes of the type trans-[M(cyclam)(C≡CCF(3))(2)]OTf (where M = Cr(3+), Co(3+), and Rh(3+); OTf = trifluoromethanesulfonate) were prepared and then characterized by electronic spectroscopy and by cyclic voltammetry for the Co(3+) complex. The UV-vis spectra for all three bear a remarkable similarity to that of the trans-M(cyclam)(CN)(2)(+) cations. The trifluoropropynyl complex of Co(3+) shows electrochemical behavior nearly identical with that of its dicyano analogue. Metal-centered phosphorescence from the Rh(III) complex in room-temperature aqueous solution has a quantum yield of 0.12 and a lifetime of 73 μs, nearly 10 times higher than those of its dicyano analogue.