The Exciting Chemistry of Tetraazidomethane

摘要

The chemistry of isocentric polyazides has experienced a renaissance in recent years.[1] Numerous homoleptic azides[2a]-[g] of the type M(N3)n as well as derivable salts[2g]-[j] have been prepared and characterized to investigate the properties of highly energetic materials. Amazingly, the organic representative tetraazidomethane (1) has not been synthesized until now, even though its structure had already been calculated at the B3LYP/6-311+G* level of theory.[3] The properties of triazidomethane, which is accessible from bromoform by simple nucleophilic substitution,[4], [5] support the expectation that 1 should be highly explosive, and thus that isolation of this homoleptic azide would be a challenge. We report herein two routes to prepare 1 as well as some of its succeeding reactions, some of which are rather surprising.