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-C
C)-chelating to one of them.