Taming the Dragon: Complexation of Silver Fulminate with Nitrogen-Rich Azole Ligands

The almost ancient and very sensitive silver fulminate (SF), which was involved in the establishment of fundamental chemical concepts, was desensitized for the first time with different nitrogen-rich triazoles and tetrazoles, yielding SF complexes [Agx(CNO)x(N-Ligand)y] (x = 1-4; y = 1-3). These were accurately characterized (X-ray diffraction, scanning electron microscopy, IR, elemental analysis, differential thermal analysis, and thermogravimetric analysis) and investigated concerning their energetic character. The highly energetic coordination compounds suddenly show, in contrast to SF, sensitivities in a manageable range and are therefore safer to handle. In particular, compounds [Ag4(CNO)4(BTRI)] [3; BTRI = 4,4'-bis(1,2,4-triazole)] and [Ag4(CNO)4(2,2-dtp)] [8; 2,2-dtp = 1,3-di(tetrazol-1-yl)propane] show values in the range of desired lead styphnate alternatives with similar energetic performances. The crystal structure experiments reveal silver cluster formation in all complexes with distinct argentophilic interactions close to 2.77 A. Furthermore, it was possible to synthesize 8 in a one-pot reaction, avoiding the isolation of highly sensitive SF.