Chlorodifluoroacetyl Isothiocyanate, ClF2CC(O)NCS: Preparation and Structural and Spectroscopic Studies
文献类型：期刊论文
| 作者 | Ramos, Luis A.1; Ulic, Sonia E.1; Romano, Rosana M.1; Vishnevskiy, Yury V.4; Mitzel, Norbert W.4; Beckers, Helmut2; Willner, Helge2; Tong, Shengrui3; Ge, Maofa3; Della Vedova, Carlos O.1 |
| 刊名 | JOURNAL OF PHYSICAL CHEMISTRY A
 |
| 出版日期 | 2013-07-11 |
| 卷号 | 117期号:27页码:5597-5606 |
| ISSN号 | 1089-5639 |
| DOI | 10.1021/jp403549f |
| 英文摘要 | Chlorodifluoroacetyl isothiocyanate, ClF2CC(O)NCS, was synthesized by the reaction of ClF2CC(O)Cl with an excess of AgNCS. The colorless product melts at -85 degrees C, and its vapor pressure follows the equation In p = -44714 (1/T) + 11.35 (p [atm], T [K] in the range -38 to 22 degrees C. The compound has been characterized by IR (gas phase, Ar matrix, and matrix photochemistry), by liquid Raman, by F-19 and C-13 NMR, gas UV-vis, and photoelectron spectroscopy (PES), by photoionization mass spectrometry (PIMS), and by gas electron diffraction (GED). The conformational properties of ClF2CC(O)NCS have been analyzed by joint application of vibrational spectroscopy, GED and quantum chemical calculations. The existence of two conformers has been detected in the gas and liquid phases, in which the C-Cl bond adopts a gauche orientation with respect to the C=O group. the C=O group is in syn- or anti-position with respect to the N=C double bond of the NCS group. The computed Delta G degrees difference between these two gauche-syn and gauche-anti forms is Delta G degrees = -0.63 kcal mol(-1) in the B3LYP/6-31G(d) approximation The most significant gas-phase structural parameters for gauche-syn. ClF2CC(O)NCS are r(e)(NC=S) 1.559(2) angstrom, r(e)(N=CS) 1.243(2) angstrom, r(e)(N-C) 1.399(7) angstrom, r(e)(C=O) 1199(2) angstrom, and angle(e) (CNC) 134.7(13)degrees. Photolysis of ClF2CC(O)NCS using an ArF excimer laser (193 nm) mainly Yields ClF2CNCS, CO, and ClC(O)CF2NCS. The valence electronic properties of the title compound were studied using PES and PLMS. The experimental first vertical ionization energy of 10.43 eV corresponds to the ejection primarily of the sulfur lone-pair electrons of the in-plane nonbonding orbital on the NCS group. |
| 语种 | 英语 |
| WOS记录号 | WOS:000321884500005 |
| 出版者 | AMER CHEMICAL SOC |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/54581]  |
| 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, CEQUINOR, UNLP CONICET, CCT La Plata,Dept Quim,Fac Ciencias Exactas, RA-1900 La Plata, Argentina 2.Berg Univ Wuppertal, Fachbereich Anorgan Chem C, D-42097 Wuppertal, Germany 3.Chinese Acad Sci, Inst Chem, State Key Struct Chem Unstable & Stable Species, Beijing 100190, Peoples R China 4.Univ Bielefeld, Lehrstuhl Anorgan Chem & Strukturchem, D-33615 Bielefeld, Germany |
| 推荐引用方式 GB/T 7714 | Ramos, Luis A.,Ulic, Sonia E.,Romano, Rosana M.,et al. Chlorodifluoroacetyl Isothiocyanate, ClF2CC(O)NCS: Preparation and Structural and Spectroscopic Studies[J]. JOURNAL OF PHYSICAL CHEMISTRY A,2013,117(27):5597-5606. |
| APA | Ramos, Luis A..,Ulic, Sonia E..,Romano, Rosana M..,Vishnevskiy, Yury V..,Mitzel, Norbert W..,...&Della Vedova, Carlos O..(2013).Chlorodifluoroacetyl Isothiocyanate, ClF2CC(O)NCS: Preparation and Structural and Spectroscopic Studies.JOURNAL OF PHYSICAL CHEMISTRY A,117(27),5597-5606. |
| MLA | Ramos, Luis A.,et al."Chlorodifluoroacetyl Isothiocyanate, ClF2CC(O)NCS: Preparation and Structural and Spectroscopic Studies".JOURNAL OF PHYSICAL CHEMISTRY A 117.27(2013):5597-5606. |
入库方式： OAI收割
来源：化学研究所
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