The syntheses of two phenylamine-based ligand systems, N(o-PhNH2)(3) and N(o-PhNHC(O)Fr-/)(3), are reported. These ligands readily coordinate to Coll to form monomeric complexes. X-ray diffraction studies establish that the [N(o-PhNC(O)Pr-/)(3)](3-) ligand stabilizes the Coll ion in a trigonal-monopyramidal coordination environment. The axial coordination site in this complex is accessible and, upon cyanide coordination, generates an electro-chemically active species.