The reactions of imines of the formula (C₆H₅)CH=NR (R = C₆H₅, i-C₃H₇) with Ti(C₅H₅)(2,4-C₇H₁₁)(PMe₃) (C₇H₁₁ = dimethylpentadienyl) lead to expulsion of the PMe₃ and coupling between the imine’s carbon atom and a single terminus of the 2,4-C₇H₁₁ ligand, resulting in C₅H₅, “diene,” and π-amide coordination in the 16 electron products. Examination of the Ti–C and C–C bonding parameters for the “diene” ligands reveals that they may be more appropriately regarded as enediyl ligands, leading to a formal +4 oxidation state for titanium. Both complexes crystallize in the triclinic space group P[`1] P\overline{1} . For the R = C₆H₅ coupling product, a = 10.4590(2) Å, b = 11.6407(2) Å, c = 17.3729(3) Å, α = 74.7610(7)°, β = 79.8600(6)°, γ = 82.2895(11)°, V = 2000.28(6) ų, D _calc = 1.293 g/cm³ at 150(1) K. For the R = i-C₃H₇ coupling product, a = 8.1039(2) Å, b = 9.4115(2) Å, c = 13.0116(4) Å, α = 88.9906(18)°, β = 73.2780(15)°, γ = 83.3088(16)°, V = 943.82(4) ų, D _calc = 1.250 g/cm³ at 150(1) K.

Structural studies of the coupling products between imines and the Ti(C₅H₅)(2,4-C₇H₁₁) (C₇H₁₁ = dimethylpentadienyl) fragment reveal significant shortening of the Ti–N bond when a more electron donating substituent is present on the nitrogen center.