Conformational and structural studies of 2,2-difluoroethylamine from temperature dependent infrared spectra of xenon solution and ab initio calculations

Variable temperature (−55 to −100 °C) studies of the infrared spectra (4000–400 cm−1) of 2,2-difluoroethylamine, F2CHCH2NH2 dissolved in liquid xenon have been carried out. From these data three of the five possible conformers have been identified and their relative stabilities obtained. The enthalpy differences have been determined among the most stable Tt conformer and the second stable conformer, Gg, to be 83 ± 8 cm−1 (0.99 ± 0.10 kJ/mol), the third stable conformer, Gt, to be 235 ± 11 cm−1 (2.81 ± 0.13 kJ/mol). The percentage of each conformer at ambient temperature is estimated to be with Tt (34 ± 1%), Gg (45 ± 1%), Gt (22 ± 1%). The first indicator is the NCCH dihedral angle (G = gauche or T = trans) and the second one (g = gauche or t = trans) is the relative position of the lone pair of electrons on the nitrogen atom with respect to the β-carbon atom. The conformational stabilities have been predicted from ab initio calculations utilizing several different basis sets up to aug-cc-pVTZ for both MP2(full) and density functional theory calculations by the B3LYP method. By utilizing previously reported microwave rotational constants along with ab initio MP2(full)/6-311+G(d,p) predicted structural values, adjusted r0 parameters have been obtained for the two most stable conformers. The determined heavy atom structural parameters for the Tt[Gg]{Gt} conformers are: the distances (Å) C1–C2 = 1.514(3) [1.507(3)] {1.512(3)}, C2–N3 = 1.452(3) [1.458(3)] {1.453(3)}, C1–F4 = 1.368(3) [1.370(3)] {1.369(3)}, C1–F6 = 1.368(3)[1.365(3)]{1.366(3)} and angles in (°) ∠N3C2C1 = 115.0(5)[108.8(5)]{114.8(5)}, ∠F4C1C2 = 110.3(5) [109.3(5)] {109.7(5)}, ∠F6C1C2 = 110.3(5) [110.0(5)] {109.9(5)}, ∠F4C1F6 = 106.5(5) [107.0(5)] {107.1(5)} and τF4C1C2N3 = 58.6(5) [64.5(5)] {61.2(5)}. Vibrational assignments have been provided for most of the observed bands which have been supported by MP2(full)/6-31G(d) ab initio calculations to predict harmonic force fields, frequencies, infrared intensities, Raman activities and depolarization ratios for the three conformers. The results are discussed and compared to the corresponding properties of some similar molecules.