Structural Analysis of Perfluoropropanoyl Fluoride in the Gas, Liquid and Solid Phases

YANINA BERRUETA MARTÍNEZ; CHRISTIAN G. REUTER; YURY V. VISHNEVSKIY; YANINA B. BAVA; A. LORENA PICONE; ROSANA M. ROMANO; HANS-GEORG STAMMLER; BEATE NEUMANN; NORBERT W. MITZEL; CARLOS O. DELLA VÉDOVA

JOURNAL OF PHYSICAL CHEMISTRY A

AMER CHEMICAL SOC

Lugar: Washington; Año: 2016 vol. 120 p. 2420 - 2430

1089-5639

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 X-ray diffraction (XRD) data reveal the presence of solely the gauche-conformation in the solid state. A set of intermolecular interactions including C═O···C═O, C?F···F?C, and F···C═O is detected. The nature of bonding and the relative stabilities of gauche- and anti-conformers are explored using natural bond orbitals.