PUB - Publikationen an der Universität Bielefeld

The coexistence of two conformers in perfluoropropanoyl fluoride, CF3CF2C(O)F, differing in the CC-CF dihedral angle (gauche 85(10)% and anti 15(10)%), has been determined by means of gas-phase electron diffraction (GED). Quantum-chemical calculations performed at the MP2 and B3LYP approximations and cc-pVTZ basis sets reproduce the experimental values with confidence. By contrast, FTIR spectra give no clear evidence for the anti-conformer in the gas phase. Information on this less abundant but stable rotamer is obtained from matrix-isolation/FTIR spectroscopy and liquid Raman spectroscopy. In situ crystallization and single-crystal Xray diffraction (XRD) data reveal the presence of solely the gauche-conformation in the solid state. A set of intermolecular interactions including C=O center dot center dot center dot C=O, C-F center dot center dot center dot F-C, and F center dot center dot center dot C=O is detected. The nature of bonding and the relative stabilities of gauche- and anti-conformers are explored using natural bond orbitals.