首页> 外文期刊>Chemistry: A European journal >Methanesulfenyl Fluoride, CH3SF, a Missing Link in the Family of Sulfenyl Halides: Formation and Characterization through the Matrix Photochemistry of Methyl Thiofluoroformate, FC(O)SCH3
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Methanesulfenyl Fluoride, CH3SF, a Missing Link in the Family of Sulfenyl Halides: Formation and Characterization through the Matrix Photochemistry of Methyl Thiofluoroformate, FC(O)SCH3

机译:甲硫基氟化物CH3SF,亚硫基卤化物家族中的缺失环节:硫代氟甲酸甲酯FC(O)SCH3的基质光化学形成和表征

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摘要

Matrix-isolation experiments have afforded the means of preparing the hitherto unknown sulfur(II) fluoride, methanesulfenyl fluoride, CH3SF. Broadband UV-visible irradiation of methyl thiofluoroformate, FC(O)SCH3, isolated in a solid Ar matrix results, first, in photoisomerization of the syn into the anti form of the molecule, and, subsequently, in the elimination of CO with the concomitant formation of CH3SF. Continued irradiation bringsabout tautomerization of this product with the detachment and migration of a hydrogen from the methyl group to give the molecular complex H2C= S centre dot centre dot centre dot HF. The changes have been monitored and the photoproducts detectedand identified by the IR spectra of the matrices, and the conclusions confirmed: 1) with reference to the corresponding behavior of the perdeuterated molecule FC(O)SCD_3; 2) by analogy with the properties of related molecules, for example, ClC(O)SCH_3, CH_3SCl, and H_2C=S centre dot centre dot centre dot HCl, and; 3) by comparison with the vibrational properties simulated for the different molecules by ab initio and density functional theory methods.
机译:基质分离实验提供了制备迄今未知的氟化硫(II),甲硫基氟化物,CH3SF的方法。固态Ar基质中分离出的硫代氟甲酸甲酯FC(O)SCH3的宽带可见光照射,首先导致syn发生光异构化为分子的反形式,随后消除伴随的CO CH3SF的形成。持续的辐照导致该产物的互变异构化,同时氢从甲基上脱离并迁移,得到分子复合物H2C = S中心点中心点中心点HF。监测了变化,并通过基质的红外光谱检测和鉴定了光产物,并得出以下结论:1)参考了氘代分子FC(O)SCD_3的相应行为; 2)与相关分子的性质类似,例如ClC(O)SCH_3,CH_3SCl和H_2C = S中心点中心点中心点HCl,和3)通过从头算和密度泛函理论方法与不同分子模拟的振动特性进行比较。

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