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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Spectroscopic characterization and constitutional and rotational isomerism of ClC(O)SCN and ClC(O)NCS
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Spectroscopic characterization and constitutional and rotational isomerism of ClC(O)SCN and ClC(O)NCS

机译：ClC（O）SCN和ClC（O）NCS的光谱表征以及组成和旋转异构

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Chlorocarbonylthio-and isothiocyanate (ClC(O)SCN and ClC(O)NCS) have been isolated and characterized by IR (Ar matrix, gas), Raman (liquid), ~(13)C NMR and UV-visible spectroscopies. Vibrational and quantum chemical studies suggest the presence of the syn and anti conformers (SCN group with respect to the Ci=O bond) in the gas phase for both constitutional isomers. syn-ClC(O)SCN is preferred by ΔH (anti/syn) = 1.3(0.3) kcal mol ~(-1). The solid-state structure of ClC(O)SCN has been determined by single crystal X-ray diffraction analysis at low temperature. The crystalline solid consists exclusively of molecules in the syn conformation. On the other hand, the anti form is more stable for the ClC(O)NCS isomer. The structure of ClC(O)NCS and its conformational composition were determined by gas electron diffraction. An unusual low syn → anti interconversion energy barrier of 0.98 (0.15) kcal mol~(-1) was detected for ClC(O)NCS at cryogenic temperatures. The photochemistry of both constitutional isomers isolated in solid argon at 15 K was studied. Rearrangement of ClC(O)SCN to ClC(O)NCS was observed in the neat liquid and under UV-vis irradiation of ClC(O)SCN isolated in solid argon. Properties have been discussed in terms of the valence electronic structure, including the analysis of the He(I) photoelectron spectrum of ClC(O)SCN.
机译：氯羰基硫代和异硫氰酸酯（ClC（O）SCN和ClC（O）NCS）已分离并通过IR（Ar基质，气体），Raman（液体），〜（13）C NMR和UV可见光谱进行了表征。振动和量子化学研究表明，两种构型异构体在气相中均存在顺式和反式构象异构体（相对于Ci = O键为SCN基）。 syn-ClC（O）SCN优选为ΔH（anti / syn）= 1.3（0.3）kcal mol〜（-1）。 ClC（O）SCN的固态结构已通过低温下的单晶X射线衍射分析确定。结晶固体仅由顺式构象的分子组成。另一方面，抗形式对于ClC（O）NCS异构体更稳定。 ClC（O）NCS的结构及其构象组成通过气体电子衍射确定。 ClC（O）NCS在低温下检测到异常的低syn→反互转换能垒为0.98（0.15）kcal mol〜（-1）。研究了在15 K下在固体氩气中分离的两种结构异构体的光化学。在纯净液体中和在固体氩气中分离的ClC（O）SCN的紫外可见光照射下，观察到ClC（O）SCN重排为ClC（O）NCS。已经针对价电子结构讨论了性质，包括对ClC（O）SCN的He（I）光电子光谱的分析。

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