Greg Drake

Preparation and vibrational spectra of N(CH3)4+IF2− and electronic structure calculations of IF2−, BrF2−, ClF2−, XeF2 and KrF2

Abstract The new IF 2 salt, N(CH 3 ) 4 IF 2 , was prepared in quantitative yield and high purity from commercially available N(CH 3 ) 4 I and XeF 2 at −31°C in CH 3 CN solution. Its vibrational spectra were recorded and, combined with correlated ab initio calculations at the MP2/SBK + (D) and CCSD(T) /SBK + (D) levels of theory for IF 2 − , BrF 2 − , ClF 2 − , XeF 2 , and KrF 2 , show that the infrared spectrum previously reported for IF 2 − is in error. The antisymmetric stretching modes in IF 2 − and BrF 2 − have lower frequencies than the symmetric ones. This highly unusual fact can be explained by mass effects and the enhancement of semi-ionic, 3 center-4 electron bonding by the antisymmetric stretching motion.

The synthesis and characterization of methylene bisoxyamine CH2(-o-NH2)2 salts

Abstract A large family of energetic salts were made using methylene bisoxyamine, CH2(-o-NH2)2, a dibasic, geminal oxyamine of methane. Single salts including the nitrate, perchlorate, dinitramide, and nitroformate, and doubly protonated methylene bisoxyamine salts, nitrate, perchlorate and bisdinitramide, were all synthesized in good to high yields, from simple acid-base reactions with the corresponding aciforms of energetic anions. All of the salts were characterized by vibrational (IR, Raman), multinuclear nmr (1H, 13C), and DSC studies. The single crystal X-ray diffraction study was carried out on the double perchlorate salt. Initial safety studies (impact and friction), were carried out on most of the new materials, as well as the thermal stability of these salts at 75°C.