Chlorodifluoroacetyl Isocyanate, ClF2CC(O)NCO: 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.2; Berger, Raphael J. F.2; Mitzel, Norbert W.2; Beckers, Helmut3; Winner, Helge3; Tong, Shengrui4; Ge, Maofa4 |
| 刊名 | JOURNAL OF PHYSICAL CHEMISTRY A
 |
| 出版日期 | 2012-11-29 |
| 卷号 | 116期号:47页码:11586-11595 |
| ISSN号 | 1089-5639 |
| DOI | 10.1021/jp3096055 |
| 英文摘要 | Chlorodifluoroacetyl isocyanate, ClF2CC(O)NCO, was prepared by the reaction of ClF2CC(O)Cl with excess of AgNCO. The colorless compound melts at -83 degrees C and the vapor pressure follows the equation In p = -3868.3 (1/T) + 10.89 (p [Atm], T [K]) in the range -38 to +22 degrees C, extrapolated bp ca. 82 degrees C. It has been characterized by IR (gas phase, Ar matrix), liquid Raman, F-19 and C-13 NMR, gas UV-vis spectrum, photoelectron spectroscopy (PES), photoionization mass spectrometry (PIMS), and gas electron diffraction (GED). The matrix photochemistry has been studied and the conformational properties of ClF2CC(O)-NCO have been analyzed by joint application of vibrational spectroscopy, GED, and quantum chemical calculations. Two conformers were detected in gaseous and liquid phases, in which the C Cl bond adopts a gauche orientation with respect to the C=O group, whereas this group can be in syn or anti orientation with respect to the N=C bond of the NCO group. An enthalpy difference Delta H degrees(exp) = 1.3 +/- 0.2 kcal mol(-1) between the most stable syn-gauche and the less stable anti-gauche form was derived using the van't Hoff equation, which is in reasonable agreement with the computed difference of Delta H degrees = 0.8 kcal mol(-1) (B3LYP/6-311+G(3df) approximation). The most significant gas phase structural parameters for gauche-syn ClF2CC(O)NCO are r(e)(NC=O) = 1.157(1) angstrom, r(e)(N=CO) = 1.218(1) angstrom, r(e)(N-C) = 1.378(9) angstrom, r(e)(C=O) = 1.195(1) angstrom, angle(e)(CNC) = 128.6(19)degrees. Photolysis of ClF2CC(O)NCO using an ArF excimer laser (193 nm) mainly yield ClF2CNCO along with some ClF2CC(O)N nitrene. The valence electronic properties of the title compound were studied using the PES and PIMS. The experimental first vertical ionization energy of 11.54 eV corresponds to the ejection of a carbonylic oxygen lone pair electron. |
| 语种 | 英语 |
| WOS记录号 | WOS:000311650200013 |
| 出版者 | AMER CHEMICAL SOC |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/49063]  |
| 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.Univ Nacl La Plata, Fac Ciencias Exactas, Dept Quim, CEQUINOR UNLP CONICET, RA-1900 La Plata, Buenos Aires, Argentina 2.Univ Bielefeld, Lehrstuhl Anorgan Chem & Strukturchem, D-33615 Bielefeld, Germany 3.Berg Univ Wuppertal, Fachbereich Anorgan Chem C, D-42097 Wuppertal, Germany 4.Chinese Acad Sci, Inst Chem, State Key Lab Struct Chem Unstable & Stable Speci, Beijing 100190, Peoples R China |
| 推荐引用方式 GB/T 7714 | Ramos, Luis A.,Ulic, Sonia E.,Romano, Rosana M.,et al. Chlorodifluoroacetyl Isocyanate, ClF2CC(O)NCO: Preparation and Structural and Spectroscopic Studies[J]. JOURNAL OF PHYSICAL CHEMISTRY A,2012,116(47):11586-11595. |
| APA | Ramos, Luis A..,Ulic, Sonia E..,Romano, Rosana M..,Vishnevskiy, Yury V..,Berger, Raphael J. F..,...&Della Vedova, Carlos O..(2012).Chlorodifluoroacetyl Isocyanate, ClF2CC(O)NCO: Preparation and Structural and Spectroscopic Studies.JOURNAL OF PHYSICAL CHEMISTRY A,116(47),11586-11595. |
| MLA | Ramos, Luis A.,et al."Chlorodifluoroacetyl Isocyanate, ClF2CC(O)NCO: Preparation and Structural and Spectroscopic Studies".JOURNAL OF PHYSICAL CHEMISTRY A 116.47(2012):11586-11595. |
入库方式： OAI收割
来源：化学研究所
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