Oligomerization of dialkylazidogallium compounds: a structural and solution-phase study

Dialkylazidogallium compounds R2GaN3(R =tBu (1), Me3SiCH2(3), iPr (5)) are prepared by reaction of the dialkylmethoxy gallium precursors with trimethylsilylazide. The reactions produce the target compounds in high purity and yield. All compounds are low-melting solids or liquids, which have no tendency to thermally decompose near their melting/boiling points. The compounds display variable degrees of oligomerization in different physical states. Compound 3 is a solid-state trimer, but exhibits a monomer-dimer equilibrium in solution. Compound 1 is a waxy solid, and appears to be composed of dimeric molecules on the basis of mass spectral, Raman and PM3 computational analyses.