Synthesis, Spectroscopic Characterization, and Conformational Properties of Trichloromethanesulfenyl Acetate, CCl3SOC(O)CH3

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• 作者：Marlene Cuaquira Reina ; Roland Boese ; Maofa Ge ; Sonia E. Ulic ; Helmut Beckers ; Helge Willner ; Carlos O. Della Vé ; dova
• 刊名：Journal of Physical Chemistry A
• 出版年：2008
• 出版时间：August 28, 2008
• 年：2008
• 卷：112
• 期：34
• 页码：7939-7946
• 全文大小：247K
• 年卷期：v.112,no.34(August 28, 2008)
• ISSN：1520-5215

文摘

Trichloromethanesulfenyl acetate, CCl₃SOC(O)CH₃, belongs to the family of sulfenic esters. This molecule has been characterized by vibrational spectroscopy. The conformational and geometrical properties of this species have been determined by IR and Raman spectroscopy, X-ray diffraction, and quantum chemical calculations. Geometry optimizations of the most stable forms were performed with ab initio (HF, MP2) and density functional theory (B3LYP) methods. According to our data, this compound results in a gauche−syn conformer with C₁ symmetry (gauche orientation around the S−O bond and syn orientation of the CO double bond with respect to the S−O single bond) for the most stable geometry, and trans−syn conformer with C_s symmetry (trans orientation around the S−O bond and syn orientation of the CO double bond with respect to the S−O single bond) for the second stable conformer (1.1 and 0.53 kcal/mol higher in energy than the most stable C₁ form according to the matrix FTIR spectroscopy and MP2/6-31G* level of the theory, respectively). The crystalline solid (monoclinic, P2₁/n, a = 8.0152(17) Å, b = 5.7922(13) Å, c = 17.429(4) Å, α = γ = 90°, β = 100.341(3)°) consists exclusively of the main form. The geometrical parameters (X-ray diffraction) are d_C−Cl = 1.767(19) Å, d_C−S = 1.797(2) Å, d_S−O = 1.663(14) Å, d_CO = 1.189(2) Å, d_O−C = 1.389(3) Å, d_C−C = 1.483(3) Å, angles Cl−C−Cl = 110.3(11)°, Cl−C−S = 111.8(12)°, C−S−O = 97.4(8)°, S−O−C = 116.7(11)°, O−CO = 122.8(19)°, OC−C = 127.1(2)°, and the main torsion angles are δ(CSOC) = 105.9(15)° and δ(SOC(O)) = 7.6(3)°. The geometrical data calculated with B3LYP/6-31G++(3df,3pd), B3LYP/6-311G++(3df,3pd), B3LYP/aug-cc-pVTZ, and MP2/6-31G* are in good agreement with diffraction data.