Chlorodifluoroacetyl Cyanide, ClF2CC(O)CN: Synthesis, Structure, and Spectroscopic Characterization

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• 作者：Luis A. Ramos ; Sonia E. Ulic ; Rosana M. Romano ; Shengrui Tong ; Maofa Ge ; Yuri V. Vishnevskiy ; Raphael J. Berger ; Norbert W. Mitzel ; Helmut Beckers ; Helge Willner ; Carlos O. Della V茅dova
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：October 3, 2011
• 年：2011
• 卷：50
• 期：19
• 页码：9650-9659
• 全文大小：975K
• 年卷期：v.50,no.19(October 3, 2011)
• ISSN：1520-510X

文摘

The novel molecule difluorochloroacetyl cyanide, ClF₂CC(O)CN, has been characterized by IR (gas phase, Ar matrix), Raman (liquid), ¹⁹F and ¹³C NMR, and photoelectron (PES) spectroscopies; photoionization mass spectrometry (PIMS); and gas electron diffraction (GED). The conformational properties of ClF₂CC(O)CN have been studied by joint application of vibrational spectroscopy, GED, and quantum chemical calculations. The existence of two conformers is detected in the gas and liquid phases, in which the C鈥揅l bond adopts gauche and syn orientations with respect to the C鈺怬 group. The computed enthalpy difference is in harmony with the experimental results of the gauche being more stable than the syn conformer by 螖H掳 = 1.3 kcal mol^鈥? (MP2/cc-pVTZ). The valence electronic properties and the possible ionization and dissociation processes of the title compound are studied using the PES and PIMS. The experimental first vertical ionization energy of 12.0 eV corresponds to the ejection of an electron of the oxygen lone pairs. Taking into account the properties and broad applications of acyl cyanides, ClF₂CC(O)CN is a promising new precursor in preparative chemistry.