Spectroscopic Characterization and Constitutional and Rotational Isomerism of ClC(O)SCN and ClC(O)NCS
文献类型：期刊论文
| 作者 | Ramos, Luis A.1; Ulic, Sonia E.1,2; Romano, Rosana M.1; Erben, Mauricio F.1; Vishnevskiy, Yury V.3; Reuter, Christian G.3; Mitzel, Norbert W.3; Beckers, Helmut4; Willner, Helge4; Zeng, Xiaoqing4 |
| 刊名 | JOURNAL OF PHYSICAL CHEMISTRY A
 |
| 出版日期 | 2013-03-21 |
| 卷号 | 117期号:11页码:2383-2399 |
| ISSN号 | 1089-5639 |
| DOI | 10.1021/jp400281g |
| 英文摘要 | Chlorocarbonylthio- and isothiocyanate (ClC(O)SCN and ClC(O)-NCS) have been isolated and characterized by IR (Ar matrix, gas), Raman (liquid), C-13 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 C=O bond) in the gas phase for both constitutional isomers. syn-ClC(O)SCN is preferred by Delta H degrees (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 elecctronic structure including the analysis of the He(I) photoelectron spectrum of ClC(O)SCN. |
| 语种 | 英语 |
| WOS记录号 | WOS:000316773200012 |
| 出版者 | AMER CHEMICAL SOC |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/42203]  |
| 专题 | 中国科学院化学研究所 |
| 通讯作者 | Della Vedova, Carlos O. |
| 作者单位 | 1.Natl Univ La Plata, Fac Ciencias Exactas, Dept Quim, CONICET,CEQUINOR, RA-1900 La Plata, Argentina 2.Univ Nacl Lujan, Dept Ciencias Basicas, RA-6700 Lujan, Argentina 3.Univ Bielefeld, Lehrstuhl Anorgan Chem & Strukturchem, D-33615 Bielefeld, Germany 4.Berg Univ Wuppertal, Fachbereich Anorgan Chem C, D-42097 Wuppertal, Germany 5.Chinese Acad Sci, Inst Chem, BNLMS, State Key Lab Struct Chem Unstable & Stable Speci, Beijing 100080, Peoples R China |
| 推荐引用方式 GB/T 7714 | Ramos, Luis A.,Ulic, Sonia E.,Romano, Rosana M.,et al. Spectroscopic Characterization and Constitutional and Rotational Isomerism of ClC(O)SCN and ClC(O)NCS[J]. JOURNAL OF PHYSICAL CHEMISTRY A,2013,117(11):2383-2399. |
| APA | Ramos, Luis A..,Ulic, Sonia E..,Romano, Rosana M..,Erben, Mauricio F..,Vishnevskiy, Yury V..,...&Della Vedova, Carlos O..(2013).Spectroscopic Characterization and Constitutional and Rotational Isomerism of ClC(O)SCN and ClC(O)NCS.JOURNAL OF PHYSICAL CHEMISTRY A,117(11),2383-2399. |
| MLA | Ramos, Luis A.,et al."Spectroscopic Characterization and Constitutional and Rotational Isomerism of ClC(O)SCN and ClC(O)NCS".JOURNAL OF PHYSICAL CHEMISTRY A 117.11(2013):2383-2399. |
入库方式： OAI收割
来源：化学研究所
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