Conformational analysis. Part 33.1 An NMR, solvation and theoretical investigation of conformational isomerism in N,N-dimethylfluoroacetamide and N,N-dimethyl-α-fluoropropionamide
Abstract
The ) at the B3LYP/6-311+G(d,p) level with ZPE (zero point energy) corrections was used to obtain the conformer geometries. In DMFA, the DFT method gave only two minima for the cis (F–C–C
O, 0°) and gauche (F–C–C
O, 140.6°) rotamers. The trans rotamer was not a minimum in the energy surface. Assuming only the cis and gauche forms, the observed couplings when analysed by solvation theory gave the energy difference (Ecis − Eg
) of 2.5 kcal mol−1 in the vapour phase, (cf. the ab initio value of 2.3 kcal mol−1) decreasing to 0.87 kcal mol−1 in
O, 30.4°), gauche-1 (F–C–C
O, 144.7°) and gauche-2 (F–C–C
O, −124.1°) rotamers with (Ecis − Eg2) equal to 2.5 kcal mol−1 and (Eg1 − Eg2) equal to 0.3 kcal mol−1. The observed couplings were analysed by solvation theory assuming one “average”
gauche conformer to give (Ecis − Eg(AV)
) equal to 2.1 kcal mol−1 in the vapour phase, decreasing to 0.83 kcal mol−1 in CCl4 and to −1.11 kcal mol−1 in