CEQUINOR (UNLP-CONICET), Departamento de Química, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, 47 esq. 115, 1900 La Plata, República Argentina.
Inorg Chem. 2011 Oct 3;50(19):9650-9. doi: 10.1021/ic201390h. Epub 2011 Aug 26.
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.
新型分子二氟一氯乙腈，ClF(2)CC(O)CN，已通过红外（气相，Ar 基质）、拉曼（液体）、（19）F 和（13）C NMR、光电子能谱（PES）光谱学；光电离质谱（PIMS）；和气体电子衍射（GED）进行了表征。ClF(2)CC(O)CN 的构象性质通过振动光谱、GED 和量子化学计算的联合应用进行了研究。在气相和液相中检测到两种构象的存在，其中 C-Cl 键相对于 C=O 基团呈 gauche 和 syn 取向。计算的焓差与 gauche 比 syn 构象更稳定的实验结果一致，ΔH° = 1.3 kcal mol(-1)（MP2/cc-pVTZ）。使用 PES 和 PIMS 研究了标题化合物的价电子性质和可能的电离和离解过程。实验得到的第一垂直电离能为 12.0 eV，对应于氧孤对电子的逐出。考虑到酰基氰化物的性质和广泛应用，ClF(2)CC(O)CN 是一种有前途的新前体在制备化学中。
