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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Trifluoromethanesulfenyl acetate, CF3S-OC(O)CH3, and trifluoromethanesulfenyl trifluoroacetate, CF3S-OC(O)CF3: Unexpected conformational properties
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Trifluoromethanesulfenyl acetate, CF3S-OC(O)CH3, and trifluoromethanesulfenyl trifluoroacetate, CF3S-OC(O)CF3: Unexpected conformational properties

机译：三氟甲硫基乙酸酯CF3S-OC（O）CH3和三氟甲硫基三氟乙酸酯CF3S-OC（O）CF3：意外的构象性质

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摘要

Structural and conformational properties of two sulfenyl derivatives, trifluoromethanesulfenyl acetate, CF3S-OC(O)CH3(1), and trifluoromethanesulfenyl trifluoroacetate, CF3S-OC(O)CF3 (2), were determined by gas electron diffraction, vibrational spectroscopy, in particular with IR (matrix) spectroscopy, which includes photochemical studies, and by quantum chemical calculations. Both compounds exist in the gas phase as a mixture of two conformers, with the prevailing component possessing a gauche structure around the S-O bond. The minor form, 15(5)% in 1 and 11(5)% in 2 according to IR(matrix) spectra, possesses an unexpected trans structure around the S-O bond. The C=O bond of the acetyl group is oriented syn with respect to the S-O bond in both conformers. UV-visible broad band irradiation of I and 2 isolated in inert gas matrixes causes various changes to occur. Conformational randomization clearly takes place in 2 with simultaneous formation of CF3SCF3. For I the only reaction channel detected leads to the formation of CH3SCF3 with the consequent extrusion Of CO2. Quantum chemical calculations (B3LYP/6-31G* and MP2 with 6-31G* and 6-311G(2df,pd) basis sets) confirm the existence of a stable trans conformer. The calculations reproduce the conformational properties for both compounds qualitatively correct with the exception of the B3LYP method for compound 2 which predicts the trans form to be prevailing, in contrast to the experiment.
机译：两种亚磺酰基衍生物的结构和构象性质分别通过气相电子衍射，振动光谱法确定使用红外（矩阵）光谱学，包括光化学研究和量子化学计算。两种化合物均以两种构象异构体的混合物形式存在于气相中，主要成分在S-O键周围具有薄纱结构。次要形式，根据IR（matrix）光谱，在1中占15（5）％，在2中占11（5）％，在S-O键周围具有意想不到的反式结构。在两个构象异构体中，乙酰基的C ＝ O键相对于S-O键为syn取向。在惰性气体基质中分离出的I和2的紫外线可见宽带照射导致发生各种变化。构象随机化明显发生在2中，同时形成了CF3SCF3。对于I，检测到的唯一反应通道导致CH3SCF3的形成，并随之挤出CO2。量子化学计算（B3LYP / 6-31G *和具有2-31G *和6-311G（2df，pd）基组的MP2）证实了稳定的反式构象体的存在。与实验相反，该计算重现了两种化合物的构象性质，在质量上均正确，但化合物2的B3LYP方法除外，该方法预测了主要的反式形式。

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