Monomeric LiPhNNPhSiMe3.2Et2O was obtained by deprotonation of PhHNNPhSiMe3 with BuLi in the presence of Et2O. Reaction of NaN(SiMe3)2 with PhHNN(SiMe3)2 in a C6H6/THF mixt. provided monomeric NaPhNN(SiMe3)2.3THF, or NaPhNN(SiMe3)2.THF using a small amt. of THF. THF can be replaced by Et2O or tBuOMe to give 1:1 solvates. These assoc., forming chains in the solid state via hn coordination (n = 2, 3) of their Ph groups to the Na centers of adjacent mols. In contrast, not only deprotonation but also desilylation occurs on reaction of NaN(SiMe3)2 with PhHNNPhSiMe3 or of NaNH2 with Me3SiHNNPh2. The latter reaction results in the formation of hexameric (NaHNNPh2)6, which adopts a face-sharing double-cubane structure. [on SciFinder (R)]