Abstract: | The title ionic solid, [Ti(C2H6N)3(C2H7N)2][Ti(C18BF15N)(C18H2BF15N)Cl(C2H7N)2]·C7H8, (I), comprises a cation with three dimethylamide ligands in the equatorial plane and two dimethylamine ligands positioned axially in a trigonal–bipyramidal geometry about the central TiIV atom. The anion has a highly distorted octahedral structure. The two dimethylamine ligands are coordinated mutually trans. The chloride is trans to the tris(pentafluorophenyl)boron–amide, while the sixth coordination site is occupied by an ortho‐F atom of the tris(pentafluorophenyl)boron–amide group in a trans disposition with respect to the tris(pentafluorophenyl)boron–nitride ligand. The most significant feature of the anion is the presence of an unprecedented terminal Ti[triple‐bond]N moiety [1.665 (2) Å], stabilized by coordination to B(C6F5)3, with a Ti[triple‐bond]N—B angle of 169.50 (19)°. |