The 1,4-dialkyl-1,4,7-triazacyclononanes HR2[9]aneN3 (R = Me or Pri) were smoothly deprotonated with n-butyllithium to give corresponding lithiated amides {Li[R2[9]aneN3]}x1, 2 which are in turn useful precursors to new transition metal complexes. Reaction of 1 or 2 with the mono(imido) or bis(imido) complexes [M(NBut)Cl3(py)2] (M = Nb or Ta) or [Mo2(NC6H3R′-2,6)2Cl2(dme)] gave [M(NBut)(R2[9]aneN3)Cl2] (M = Nb, R = Me 3 or Pri4; M = Ta, R = Me 5 or Pri6) or [Mo(NC6H3R′2-2,6)2(R2[9]aneN3)Cl] (R = Me, R′ = Pri8; R = Pri, R′ = H 9, Me 10 or Pri11). The compounds 3–6 are relatives of the d0 metallocene dichlorides [M(η-C5R5)2Cl2] (M = Group 4 metal). The titanium imido analogue [Ti(NBut)(HPri2[9]aneN3)Cl2] 7 has been prepared for purposes of comparison and exists as a mixture of isomers in solution. The crystal structure of the bis(imido) compound 11 has been determined and shows that the co-ordination of the amido N-donor of Pri2[9]aneN3 is not greatly distorted from planarity. Examination of the molecular structure suggests that in this compound the Pri2[9]aneN3 ligand acts effectively as a 5-electron donor with the molybdenum dπ-acceptor orbitals dominated by the strongly π-donating arylimido ligands. Extrapolation to the mono(imido) complexes [M(NBut)(R2[9]aneN3)Cl2] 3–6, in which the amido N-donor of Pri2[9]aneN3 lies trans to one of the Cl ligands and cis to NBut, suggests that the amido N-donor should be able at least partly to π-donate to the metal centres. Hence in 3–6 the Pri2[9]aneN3 ligand can in principle act as up to a 7-electron donor.