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
✍ Scribed by Rosana M. Romano; Carlos O. Della Védova; Anthony J. Downs
- Publisher
- John Wiley and Sons
- Year
- 2007
- Tongue
- English
- Weight
- 176 KB
- Volume
- 13
- Category
- Article
- ISSN
- 0947-6539
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✦ Synopsis
Abstract
Matrix‐isolation experiments have afforded the means of preparing the hitherto unknown sulfur(II) fluoride, methanesulfenyl fluoride, CH~3~SF. Broadband UV‐visible irradiation of methyl thiofluoroformate, FC(O)SCH~3~, 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 CH~3~SF. Continued irradiation brings about tautomerization of this product with the detachment and migration of a hydrogen from the methyl group to give the molecular complex H~2~CS⋅⋅⋅HF. The changes have been monitored and the photoproducts detected and 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~3~SCl, and H~2~CS⋅⋅⋅HCl, and; 3) by comparison with the vibrational properties simulated for the different molecules by ab initio and density functional theory methods.