首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Photochemical Reaction Channels of OCS with Cl_2,ICl,or IBr Isolated Together in an Argon Matrix:Isolation of syn-Iodocarbonylsulfenyl Bromide
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Photochemical Reaction Channels of OCS with Cl_2,ICl,or IBr Isolated Together in an Argon Matrix:Isolation of syn-Iodocarbonylsulfenyl Bromide

机译:在氩气基质中一起分离出带有Cl_2,ICl或IBr的OCS的光化学反应通道:溴化同碘羰基亚硫基的分离

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摘要

The photolytically induced reactions of a dihalogen XY (= Cl_2,ICl,or IBr) with OCS isolated together in an Ar matrix at about 15 K lead to different photoproducts depending on the natures of X and Y.In addition to the known species ClCO~(centre dot),OCCl_2,syn-ClC(O)SCl,syn-ClC(O)SSCl,IC(O)Cl,IC(O)Br,and syn-BrC(O)SBr,syn-iodocarbonylsulfenyl bromide,syn-IC(O)SBr,has thus been identified for the first time as a photoproduct of the reactions involving IBr.The first product to be formed in the reactions with Cl_2 or ICl is the ClCO~(centre dot) radical which reacts subsequently with halogen or sulfur atoms or other matrix guests to give the corresponding carbonyl dihalide (OCCl_2 and IC(O)Cl),syn-ClC(O)SCl or syn-ClC(O)SSCl.The analogous reaction with IBr affords syn-BrC(O)SBr,IC(O)Br,and syn-IC(O)SBr.The changes have been followed,the products characterized experimentally by IR measurements,and the spectra analyzed in the light of the results of appropriate theoretical calculations.
机译:在X射线和Y射线的性质下,大约15 K的Ar矩阵中一起分离出的二卤素XY(= Cl_2,ICl或IBr)与OCS的光解诱导的反应会产生不同的光产物。 (中心点),OCCl_2,syn-ClC(O)SCl,syn-ClC(O)SSCl,IC(O)Cl,IC(O)Br,和syn-BrC(O)SBr,syn-碘代羰基亚磺酰基溴,syn因此,首次将-IC(O)SBr鉴定为涉及IBr的反应的光产物。在与Cl_2或ICl的反应中形成的第一个产物是ClCO〜(中心点)自由基,其随后与卤素或硫原子或其他基质客体得到相应的羰基二卤化物(OCCl_2和IC(O)Cl),syn-ClC(O)SCl或syn-ClC(O)SSCl。与IBr的类似反应得到syn-BrC(观察到了变化,通过红外测量对产物进行了实验表征,并根据适当的理论计算结果对光谱进行了分析。

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