The trifluoropropynyl ligand -C CCF3 was studied as a possible surrogate for the cyano ligand. Complexes of the type trans-[M(cyclam)(C CCF3)(2)]OTf (where M = Cr3+, Co3+, and Rh3+; OTf = trifluoromethanesulfonate) were prepared and then characterized by electronic spectroscopy and by cyclic voltammetry for the Co3+ 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 Co3+ 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 mu s, nearly 10 times higher than those of its dicyano analogue.