Triamidoamine complexes of niobium where E = O, NSiMe(3) can be prepared by treating NbOCl3(THF)(2) or Nb(NSiMe(3))Cl-3(py)(2), respectively, with Li-3[(Me(3)-SiNCH2CH2)(3)N] (Li-3[N3N]). [N3N]Nb=O reacts with excess triethylaluminum to yield [N3N]Nb=O . AlEt(3), with Me(3)SiX (X = OTf, I) to yield [N3N]NbOSiMe(+)X(-) (4), and with methyl triflate to afford [N3N]NbOMe(+)OTf(-) (5). Reduction of 4 or 5 with sodium amalgam in tetrahydrofuran yields [N3N]NbOR (R = SiMe(3), Me).