Reactions of the lithiated diamido-pyridine and -amine ligands Li₂N₂^TMSN_py or Li₂N₂N^C2,TMS with ScCl₃ in tetrahydrofuran (THF) afforded the five-coordinate scandium chloride derivatives [Sc(N₂^TMSN_py)Cl(THF)] 1 and [Sc(N₂N^C2,TMS)Cl(THF)] 2 where N₂^TMSN_py = MeC(2-C₅H₄N)(CH₂NSiMe₃)₂ and N₂N^C2,TMS = Me₃SiN(CH₂CH₂NSiMe₃)₂. The corresponding reactions of ScCl₃ with the dilithium salts of the amino N-methylated two-carbon analogue N₂N^C2,Me (N₂N^C2,Me = MeN(CH₂CH₂NSiMe₃)₂) or of the amino N-silylated three-carbon chain analogue N₂N^C3,TMS (N₂N^C3,TMS = Me₃SiN(CH₂CH₂CH₂NSiMe₃)₂) afforded no tractable products. In contrast, reaction of ScCl₃with the homologous N-methylated three-carbon chain species Li₂N₂N^C3,Me (N₂N^C3,Me = MeN(CH₂CH₂CH₂NSiMe₃)₂) cleanly gave the THF-free dinuclear, chloride-bridged compound [Sc₂(N₂N^C3,Me)₂(μ-Cl)₂] 3. The compounds 1–3 have been crystallographically characterised. Organometallic analogues of 1 and 2 have been prepared by protonolysis reactions of H₂N₂^R′N_py (N₂^R′N_py = MeC(2-C₅H₄N)(CH₂NR′)₂ where R′ = SiMe₃, Tol (4-C₆H₄Me) or Mes (2,4,6-C₆H₂Me₃)) and H₂N₂N^C2,R′ (R′ = Me or SiMe₃) with [ScR₃(THF)₂] (R = CH₂SiMe₃ or Ph) in benzene which gave the five-coordinate alkyl or phenyl compounds [Sc(N₂^R′N_py)R(THF)] (R = CH₂SiMe₃, R′ = SiMe₃ 4, Tol 5 or Mes 6; R = Ph, R′ = SiMe₃ 7) and [Sc(N₂N^C2,R′)(CH₂SiMe₃)(THF)] (R′ = Me 8 or SiMe₃ 9). The compound 4 can also be prepared by the reaction of 1 with LiCH₂SiMe₃. Reaction of [Sc(CH₂SiMe₃)₃(THF)₂] with H₂N₂N^C3,Me afforded no tractable product, and with H₂N₂N^C3,TMS in deuterobenzene the labile compound [Sc(N₂N^C3,TMS)(CH₂SiMe₃)(THF)] 10 was observed by ¹H NMR spectroscopy but could not be isolated. On one occasion the THF-free dimeric alkyl species [Sc₂(N₂^TolN_py)₂(CH₂SiMe₃)₂] 11 was obtained. This compound possesses one bridging and one terminal amido nitrogen per N₂^TolN_py ligand. The X-ray crystal structures of 6 and 11 have been determined. The monomeric compounds 1, 2 and 6 all have trigonal bipyramidal Sc centres in the solid state; the neutral donors take up the axial sites, and the amido nitrogens and either Cl or CH₂SiMe₃ occupy the equatorial ones.