A number of metal complexes containing one of the following ligands: the 1-azaallyl [N(R)C(Ph)C(H)R]⁻ (L⁻), the 1,3-diazaallyl(≡ LL′⁻) and the isomeric β-diketiminate [{N(R)C(Ph)]}₂CH]⁻ (≡ LL⁻) have been prepared (R = SiMe₃). These are the crystalline compounds H(LL) (2), Na(LL) (3), [Na(LL)(thf)₂] (4), Na(L) (6), [Na(µ-LL′)]₈ (7), [K(µ-L)(η⁶-C₆H₆)]₂ (8), [K(µ-LL′)(thf)]₂ (9), [K(thf)₂(µ-LL)]_∞ (10) and [Ni(LL′)₂] (11). A new synthesis of Na[C(H)R₂] (1) involved Hg[C(H)R₂]₂ and Na/Hg as reagents. The β-diketimine 2 was obtained from Li(LL) and cyclopentadiene. Under different conditions compounds 3, 6 and 7 were isolated from 1 and benzonitrile, and compounds 8, 9 and 10 from K[C(H)R₂] and PhCN. Complex 11 was derived from [Li(LL′)]₂ and [NiBr₂(dme)]. The solution obtained from 1 + 2 PhCN in Et₂O at ambient temperature was a mixture (5) of 3 (predominantly) and 7. The 1-azaallyl complex 8 has the ligand bound to the metal as the enamide, and this is also probably (NMR) the case for 6. The molecular structures of the crystalline complexes 7, 8 and 11 are presented; that of 10 was published earlier. Compound 7, a cyclooctamer, is particularly interesting, in that each LL′⁻ ligand is bridging via one of its N atoms to two neighbouring sodium ions and is not only N,N′- but also (η²-CC)-chelating to one of them.