Strong and very strong hydrogen bonding in fluoro-amine–fluoride systems

The formation of strong and very strong hydrogen bonds between NFnH3−n (n = 0.2) and F− have been computationally investigated via B3LYP/6-311++G(d,p) geometry optimizations and MP2/6-311++G(d,p) single point energy calculations. The enthalpy of deprotonation of NF2H was found to be 1518.5 kJ mol−1. The hydrogen bond energy in NH3⋯F−, NFH2⋯F− and NF2H⋯F− were calculated to be 67.9, 120.2 and 181.2 kJ mol−1, respectively, and clearly show the effect of fluorination on hydrogen bond strength in amine–fluoride systems. The change in enthalpy and entropy for the clustering of methanol to NF2H⋯F− to form the fluoride bound dimer of methanol and difluoramine has been measured via high pressure mass spectrometry to be 68.3 kJ mol−1 and 90.5 J K−1 mol−1. These values are in excellent agreement with calculated values of 70.9 kJ mol−1 and 88.5 J K−1 mol−1.