New groups 4 and 5 imido complexes derived from the diamidoamine ligand Me3SiN(CH2CH2NSiMe3)2 (N2N) are described. Reactions of Li2[N2N] with [Ti(NR)Cl2(py)3] gave compound 1 in which the N2N ligand adopts a fac-coordination mode. With [Nb(NtBu)Cl3(py)2], two different Nb(V) products were formed.