The reactions of NbCl5 with limited amounts (1-2 molar equivalents) of a series of primary, secondary and tertiary amines were investigated in dichloromethane as solvent. The 1:1 reaction of NbCl5 with NHEt2 cleanly afforded an equimolar mixture of [NbCl4(NEt2)](2), 1, and [NH2Et2][NbCl6], 2a; the former product constitutes the first example of structurally characterized Nb(V) chlorido-amido complex. The ammonium salts [(NH3Pr)-Pr-n][NbCl6], 2b, and [(NH2Pr2)-Pr-i][NbCl6], 2c, were isolated in 20-30% yields from the 1:1 reactions of NbCl5 with (NH2Pr)-Pr-n and (NHPr2)-Pr-i, respectively. C alpha-H bond activation and Nb(V) to Nb(IV) reduction took place in the reactions of NbCl5 with NR3 (R = Bz, Et; Bz = CH2Ph). The iminium salt [(PhCH2)(2)N=CHPh][NbCl6], 3, and the ammonium ion [NH(CH2Ph)(3)] were identified as the prevalent species generated from the 1:1 NbCl5/NBz(3) interaction. [NHEt3][NbCl6], 4, and [NHEt3](2)[NbCl6], 5, were isolated in moderate yields from, respectively, the 1:1 and 1:2 molar reactions of NbCl5 with NEt3. The solid state structures of 1, 2a, 3, 4 and 5 were ascertained by single crystal X-ray studies.