Methanesulfonyl Azide: Molecular Structure and Photolysis in Solid Noble Gas Matrices

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• 作者：Guohai Deng ; Dingqing Li ; Zhuang Wu ; Hongmin Li ; Eduard Bernhardt ; Xiaoqing Zeng
• 刊名：Journal of Physical Chemistry A
• 出版年：2016
• 出版时间：July 21, 2016
• 年：2016
• 卷：120
• 期：28
• 页码：5590-5597
• 全文大小：420K
• 年卷期：0
• ISSN：1520-5215

文摘

The parent sulfonyl azide CH₃SO₂N₃ has been characterized in a neat form by IR (gas, matrix-isolation) and Raman (solid) spectroscopy, and its structure has been established by X-ray crystallography. In both gas phase and solid state, the azide exhibits single conformation with the azido ligand being synperiplanar to one of the two S═O groups. In the crystal molecules of CH₃SO₂N₃ are interconnected through three-dimensional O···H–C–H···O hydrogen bonds. Upon an ArF laser (193 nm) photolysis, the azide in solid noble gas matrices splits off N₂ and yields the sulfonyl nitrene CH₃SO₂N in the triplet ground state. Subsequent photolysis with UV light (266 nm) causes the transformation from the nitrene to the pseudo-Curtius rearrangement product CH₃NSO₂. The identification of the photolysis intermediates by matrix-isolation IR spectroscopy is supported by quantum chemical calculations with DFT methods.