Silyl stabilized azanes: Reactions of mono- and dilithium bis(trimethylsilyl)hydrazide with dichloro- and tetrachlorostannane

SnCl4 acts primarily as an oxidant and oxidizes monolithium bis(trimethylsilyl) hydrazide 1 to mainly bis(trimethylsilyl)amine, BSA and tris(trimethylsilyl)hydrazine, TrSH and itself get reduced to SnCl2. Similarly, reaction of SnCl4 with dilithiumbis(trimethylsilyl) hydrazide 2, oxidizes it to lithium tris(trimethylsilyl)hydrazide, Li-TrSH. Reaction of dichlorostannane (reduction of oxidation state of tin from +4 to +2) with 1 gives a simple substitution reaction and give a pale yellow solid, 1,4-bis(trimethylsilyl)-1,2,4,5-tetraza-3,6-distannacyclohexane, 3b. Whereas, in reaction of 2 with SnCl2 intermediate stannimine [(Me3Si)2N–NSn], tetramerizes and further loses tetrakis(trimethylsilyl)tetrazene, TST to give a cubane compound [(Me3Si)N–Sn]4, 4.

Graphical abstractReaction of monolithiumbis(trimethylsilyl)hydrazide with dichlorostannane gives a substitution product, 1,4-bis(trimethylsilyl)-1,2,4,5-tetraza-3,6-distannacyclohexane. Whereas, the reaction of dilithium bis(trimethylsilyl)hydrazide with SnCl2 gives a pale yellow product, [(Me3Si)N–Sn]4, the first inorganic cuboid entirely build up of tin and nitrogen atoms synthesized from hydrazide moiety.Figure optionsDownload full-size imageDownload as PowerPoint slide