Azatitanatrane [Ti(i-PrNCH2CH2)(2)NCH2CH2N](2) (13) is obtained in 44% yield by the reaction of Ti(NMe(2))(4) with the new ligand (i-PrNHCH2CH2)(2)NCH2CH2NH2. Compound 13, which features a dimeric structure as determined by H-1, C-13{H-1}, and (HH)-H-1-H-1 NOESY NMR techniques and mass spectroscopy, exhibits a rigid configuration in solution on the NMR time scale. The structure of the azatitanatrane Me(2)NTi(MeNCH(2)CH(2))(3)N (1) was determined by single-crystal X-ray crystallography and was shown to exhibit unusually short axial Ti-N bonds. Crystal data : monoclinic, space group P2(1)/c, a = 7.9550(7) Angstrom, b = 10.546(2) Angstrom, c = 18.105(2) Angstrom, beta = 97.365(8)degrees, V = 1506.4(3) Angstrom(3), Z = 4, R = 0.0373.