Synthesis and Structures of Sodium Phenylhydrazides

Monomeric Li(Ph)NN(Ph)SiMe3 · 2 OEt2 was obtained by deprotonating the respective hydrazine with nBuLi in the presence of diethyl ether. Reaction of NaN(SiMe3)2 with PhHN−N(SiMe3)2 in a benzene/tetrahydrofuran mixture provided monomeric Na(Ph)NN(SiMe · 3 THF, or Nd(Ph)NN(SiMe3)2 · THF using a small amount of THE Its TI IF ran be replaced by diethyl ether or tert‐butyl methyl ether to give 1:l solvates. These associate, forming chains in the solid state via ηn coordination (n = 2, 3) of their phenyl groups to the sodium centers of adjacent molecules. In contrast, not only deprotonation but also desilylation occurs on reaction of NaN(SiMe3)2 with H(Ph)NN(Ph)SiMe3 or of NaNH2 with (Me3Si)HNNPh2) The latter reaction results in the formation ot hexameric (NaHNNPh2)6 which adopts a face‐sharing double‐cubane structure.