ICCAS OpenIR
Matrix Photochemistry, Photoelectron Spectroscopy, Solid-Phase Structure, and Ring Strain Energy of beta-Propiothiolactone
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
2009-04-16
Source PublicationJOURNAL OF PHYSICAL CHEMISTRY A
ISSN1089-5639
Volume113Issue:15Pages:3662-3672
AbstractThe 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.
DOI10.1021/jp811480v
Indexed BySCI
Language英语
WOS IDWOS:000265030400033
PublisherAMER CHEMICAL SOC
Citation statistics
Cited Times:12[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://ir.iccas.ac.cn/handle/121111/66622
Collection中国科学院化学研究所
Corresponding AuthorErben, Mauricio F.
Affiliation1.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
Recommended Citation
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.
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