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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Methanesulfonyl Azide: Molecular Structure and Photolysis in Solid Noble Gas Matrices
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Methanesulfonyl Azide: Molecular Structure and Photolysis in Solid Noble Gas Matrices

机译：甲磺酰叠氮化物：固体稀有气体基质中的分子结构和光解

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摘要

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 center dot center dot center dot H-C-H center dot center dot center dot O hydrogen bonds. Upon an ArF laser (193 nm) photolysis, the azide in solid noble gas matrices splits off N-2 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.
机译：母体磺酰叠氮化物CH3SO2N3已通过IR（气体，基质分离）和拉曼（固体）光谱以纯净形式表征，其结构已通过X射线晶体学确定。在气相和固态下，叠氮化物均表现出单一构型，叠氮基配体与两个S ＝ O基团之一在同一平面上。在CH 3 SO 2 N 3的晶体分子中，通过三维O中心点中心点中心点H-C-H中心点中心点中心点O氢键相互连接。在ArF激光（193 nm）上进行光解后，固体稀有气体基质中的叠氮化物会分离N-2并生成三重态基态的磺酰基亚硝基CH3SO2N。随后用紫外光（266 nm）进行光解会导致从腈转化为拟Curtius重排产物CH3NSO2。通过DFT方法进行量子化学计算可支持通过基质隔离红外光谱法鉴定光解中间体。

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