Matrix Photochemistry, Photoelectron Spectroscopy, Solid-Phase Structure, and Ring Strain Energy of beta-Propiothiolactone
文献类型：期刊论文
| 作者 | Dugarte, Nahir Y.1; Erben, Mauricio F.1; Romano, Rosana M.1; Boese, Roland2; Ge, Mao-Fa3; Li, Yao3; Della Vedova, Carlos O.1,4 |
| 刊名 | JOURNAL OF PHYSICAL CHEMISTRY A
 |
| 出版日期 | 2009-04-16 |
| 卷号 | 113期号:15页码:3662-3672 |
| ISSN号 | 1089-5639 |
| DOI | 10.1021/jp811480v |
| 英文摘要 | The four-membered heterocyclic beta-propiothiolactone compound was isolated in a low-temperature inert Ar matrix, and the UV-visible (200 <= lambda <= 800 nm) induced photochemistry was studied. On the basis of the IR spectra, the formation of methylketene (CH(3)CH=C=O) was identified as the main channel of photodecomposition. The formation of ethene and thiirane, with the concomitant elimination of OCS and CO, respectively, was also observed as minor decomposition channels. The valence electronic structure was investigated by HeI photoelectron spectroscopy assisted by quantum chemical calculations at the OVGF/6-311++G(d,p) level of theory. The first three bands at 9.73, 9.87, and 12.06 eV are ascribed to the n ''(s), n'(o), and pi ''(C=O) orbitals, respectively, denoting the importance of the -SC(O)(-) group in the outermost electronic properties. Additionally, the structure of a single crystal,grown in situ, was determined by X-ray diffraction analysis at low temperature. The crystalline solid [monoclinic system, P21/c, a = 8.1062(1) angstrom, b = 10.3069(2) angstrom, c = 10.2734(1) angstrom, beta = 107.628(1)degrees, and Z = 8] consists of planar molecules arranged in layers. The skeletal parameters, especially the valence angles [(sic)C2-C1-S = 94.55(7)degrees, (sic)O=C-C = 134.20(11)degrees, (sic)C-S-C = 77.27(5)degrees], differ from those typically found in acyclic thioester compounds, suggesting the presence of strong strain effects. The conventional ring strain energy was determined to be 16.4 kcal/mol at the G2MP2 level of calculation within the hyperhomodesmotic model. |
| 语种 | 英语 |
| WOS记录号 | WOS:000265030400033 |
| 出版者 | AMER CHEMICAL SOC |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/66621]  |
| 专题 | 中国科学院化学研究所 |
| 通讯作者 | Erben, Mauricio F. |
| 作者单位 | 1.Univ Nacl La Plata, Fac Ciencias Exactas, Dept Quim, CEQUINOR CONICET CCT La Plata, RA-1900 La Plata, Argentina 2.Univ Duisburg Essen, Inst Anorgan Chem, D-45117 Essen, Germany 3.Chinese Acad Sci, Inst Chem, State Key Lab Struct Chem Unstable & Stable Speci, Beijing 100080, Peoples R China 4.Univ Nacl La Plata, Fac Ciencias Exactas, Dept Quim, LaSelSiC CIC CONICET, Gonnet, Argentina |
| 推荐引用方式 GB/T 7714 | Dugarte, Nahir Y.,Erben, Mauricio F.,Romano, Rosana M.,et al. Matrix Photochemistry, Photoelectron Spectroscopy, Solid-Phase Structure, and Ring Strain Energy of beta-Propiothiolactone[J]. JOURNAL OF PHYSICAL CHEMISTRY A,2009,113(15):3662-3672. |
| APA | Dugarte, Nahir Y..,Erben, Mauricio F..,Romano, Rosana M..,Boese, Roland.,Ge, Mao-Fa.,...&Della Vedova, Carlos O..(2009).Matrix Photochemistry, Photoelectron Spectroscopy, Solid-Phase Structure, and Ring Strain Energy of beta-Propiothiolactone.JOURNAL OF PHYSICAL CHEMISTRY A,113(15),3662-3672. |
| MLA | Dugarte, Nahir Y.,et al."Matrix Photochemistry, Photoelectron Spectroscopy, Solid-Phase Structure, and Ring Strain Energy of beta-Propiothiolactone".JOURNAL OF PHYSICAL CHEMISTRY A 113.15(2009):3662-3672. |
入库方式： OAI收割
来源：化学研究所
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