X-ray crystallographic, FT-IR, and density functional theory studies of the salt formed between dipicrylamine and 1,5,7-triazabicyclo[4.4.0]dec-1-ene

Abstract

The DPA-TBD (dipicrylamine-1,5,7-triazabicyclo[4.4.0]dec-1-ene) salt has been synthesized and characterized by FT-IR spectroscopy, X-ray single-crystal diffraction, and theoretical study. In the FT-IR spectrum of the crystalline DPA-TBD salt, an unexpected intense band at 1742 cm(-1) is present. The optimized geometry and the FT-IR spectra of the DPA salt were calculated at the B3LYP/6-31G+(d) level and give an explanation of the nature of this band as the ν(C═N═C) vibration. For comparison, the calculated IR spectra of the DPA anion, hydrogen-bonded DPA anion, and neutral DPA and TBD molecules as well as for the TBD cation are also shown. The presence of the free DPA anion in the gas phase was directly detected in the negative ion mode electrospray ionization MS spectra. The fragmentation of the DPA anion is also discussed.