Reaction of AgN3 with SOCl2: Evidence for the Formation of Thionyl Azide, SO(N3)2

Pure thionyl azide SO(N3)2, which is the only gaseous reaction product, has been generated in a vacuum by the heterogeneous reaction of SOCl2 vapor with AgN3 at room temperature at a SOCl2 vapor pressure of 1 × 10-3 Torr. Evidence for the formation of SO(N3)2 is given by on line photoelectron spectroscopy (PES) combined with outer valence Green's function (OVGF) calculations with the 6-311++G(2df) basis set. The good agreement between the PES experiment and the OVGF calculation shows that SO(N3)2 has C1 symmetry. The first ionization energy of SO(N3)2 is 10.18 eV

Reaction of (COCl)2 with AgN3: Evidence for the Formation of Oxalyl Diazide O2C2(N3)2

Oxalyl diazide O2C2(N3)2 has been generated in the heterogeneous reaction of (COCl)2 vapor with AgN3 at room temperature. Evidence for the formation of O2C2(N3)2 is based on on-line photoelectron spectroscopy (PES) characterization combined with the density functional B3LYP and outer valence Green’s function (OVGF) calculations. The good agreement between the experimental spectra and theoretical calculation shows that O2C2(N3)2 has adiabatic ionization energy of 10.11 eV. Our results also suggest that O2C2(N3)2 has high conformational flexibilities and that the planar conformers are energy-favorable in gas phas