SYNTHESIS AND STRUCTURES OF SODIUM PHENYLHYDRAZIDES

Monomeric Li(Ph)N-N(Ph)SiMe3 . 2 OEt2 was obtained by deprotonating th e respective hydrazine with nBuLi in the presence of diethyl ether. Re action of NaN(SiMe3)(2) with PhHN-N(SiMe3)(2) in a benzene/tetrahydrof uran mixture provided monomeric Na(Ph)N-N(SiMe3)(2) . 3 THF, or Na(Ph) N-N(SiMe3)(2) . THF using a small amount of THF. Its THF can be replac ed by diethyl ether or tert-butyl methyl ether to give 1:1 solvates. T hese associate, forming chains in the solid state via eta(n) coordinat ion (n = 2, 3) of their phenyl groups to the sodium centers of adjacen t 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 NaNH 2 with (Me3Si)HN-NPh2. The latter reaction results in the formation of hexameric (NaHN-NPh2)(6), which adopts a face-sharing double-cubane s tructure.