title: Chlorodifluoroacetyl cyanide, ClF2CC(O)CN: synthesis, structure, and spectroscopic characterization.
abstract: The novel molecule difluorochloroacetyl cyanide, ClF(2)CC(O)CN, has been characterized by IR (gas phase, Ar matrix), Raman (liquid), (19)F and (13)C NMR, and photoelectron (PES) spectroscopies; photoionization mass spectrometry (PIMS); and gas electron diffraction (GED). The conformational properties of ClF(2)CC(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-Cl bond adopts gauche and syn orientations with respect to the C═O group. The computed enthalpy difference is in harmony with the experimental results of the gauche being more stable than the syn conformer by ΔH° = 1.3 kcal mol(-1) (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, ClF(2)CC(O)CN is a promising new precursor in preparative chemistry.
authors.affiliation: CEQUINOR (UNLP-CONICET), Departamento de Química, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, 47 esq. 115, 1900 La Plata, República Argentina.
authors.forename: Luis A
authors.initials: LA
authors.lastname: Ramos
authors.forename: Sonia E
authors.initials: SE
authors.lastname: Ulic
authors.forename: Rosana M
authors.initials: RM
authors.lastname: Romano
authors.forename: Shengrui
authors.initials: S
authors.lastname: Tong
authors.forename: Maofa
authors.initials: M
authors.lastname: Ge
authors.forename: Yuri V
authors.initials: YV
authors.lastname: Vishnevskiy
authors.forename: Raphael J
authors.initials: RJ
authors.lastname: Berger
authors.forename: Norbert W
authors.initials: NW
authors.lastname: Mitzel
authors.forename: Helmut
authors.initials: H
authors.lastname: Beckers
authors.forename: Helge
authors.initials: H
authors.lastname: Willner
authors.forename: Carlos O
authors.initials: CO
authors.lastname: Della Védova