Organobismuth compounds : V. Preparation,characterization, and properties of triphenylbismuth diazide and dicyanide

Triphenylbismuth diazide and the dicyanide have been prepared and characterized. Previously reported triphenylbismuth hydroxide cyanide has been shown to be triphenylbismuth dicyanide. A trigonal bipyramidal structure is indicated for both the compounds on the basis of their infrared and laser Raman spectra. The molecular weight and conductance data for the diazide in acetone are also in accord with a molecular structure. The dicyanide is, however, decomposed in solution into diphenylbismuth cyanide and benzonitrile. Thermal decomposition of the solid dicyanide and the diazide has also been studied. The possibility of the conversion of the diazide and the dicyanide into the corresponding dicyanate has been explored. Unlike transition metal azides, the triphenylbismuth diazide does not react with CO. Triphenylbismuth dicyanide could also not be converted into the corresponding dicyanate by reaction with either HgO or MnO₂. Reaction with HgO afforded triphenylbismuth oxide and the reaction with MnO₂ gave uncharacterized products.