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

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• 作者：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
• 刊名：Journal of Physical Chemistry A
• 出版年：2016
• 出版时间：April 21, 2016
• 年：2016
• 卷：120
• 期：15
• 页码：2420-2430
• 全文大小：678K
• 年卷期：0
• ISSN：1520-5215

文摘

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.