Vibrational spectra of ?-thiopropiolactone

Kuz'yants, G. M.

doi:10.1007/bf00747271

Cited by 4 publications

(7 citation statements)

References 9 publications

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“…This agreement is demonstrated in Figure 6, where the gas-phase and argon matrix IR spectra are shown, together with the calculated IR spectrum at the B3LYP/augcc-pVTZ level. The new results are consistent with the earlier ones 10 and reveal significantly more details, giving confidence to the proposed band assignment.…”

Section: Resultssupporting

confidence: 90%

“…The final purity in both the vapor and liquid phase was carefully checked by reference to the IR, CG-MS, and 1 H and 13 C NMR spectra. 10 Instrumentation. IR absorption spectra in the gaseous state were recorded with a resolution of 1 cm -1 in the range of 4000-400 cm -1 using a Bruker model EQUINOX 55 equipped with DLATGS detector (for the ranges 7500-370 cm -1 ) with a KBr window.…”

Section: Methodsmentioning

confidence: 99%

“…Simple non- or alkyl-substituted thiolactones have been the subject of a vast and still-growing number of studies. Structural − and vibrational analyses as well as kinetics aspects and NMR properties have been studied by experimental and theoretical methods.…”

Section: Introductionmentioning

confidence: 99%

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Matrix Photochemistry, Photoelectron Spectroscopy, Solid-Phase Structure, and Ring Strain Energy of β-Propiothiolactone

et al. 2009

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The four-membered heterocyclic beta-propiothiolactone compound was isolated in a low-temperature inert Ar matrix, and the UV-visible (200 < or = lambda < or = 800 nm) induced photochemistry was studied. On the basis of the IR spectra, the formation of methylketene (CH(3)CHCO) 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''(CO) 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) A, b = 10.3069(2) A, c = 10.2734(1) A, beta = 107.628(1) degrees, and Z = 8] consists of planar molecules arranged in layers. The skeletal parameters, especially the valence angles [angleC2-C1-S = 94.55(7) degrees, angleOC-C = 134.20(11) degrees, angleC-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.

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Section: Resultssupporting

confidence: 90%

Section: Methodsmentioning

confidence: 99%

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Matrix Photochemistry, Photoelectron Spectroscopy, Solid-Phase Structure, and Ring Strain Energy of β-Propiothiolactone

et al. 2009

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“…This last observation is in agreement with the quantum chemical calculations, which compute a very low absorption intensity at 655 cm -1 (B3LYP/aug-cc-pVTZ) for this vibrational mode. Vibrational data for the β-propio- 17,39 and γ-butyrothiolactones 18 have already been reported. Relevant vibrational data for these thiolactone species are collected in Table 4.…”

Section: Resultsmentioning

confidence: 97%

Molecular and Electronic Structure of δ-Valerothiolactone

et al. 2010

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The crystal structure of the six-member heterocyclic δ-valerothiolactone (1-thiocycloalkan-2-one) compound has been determined by X-ray diffraction at low temperature, revealing that its skeleton adopts a half-chair conformation. The conformation around the thioester group is almost planar with an anti orientation of the C=O double bond with respect the S-C single bond [C(2)-S(1)-C(6)-O(1) = 176.26(8)°]. The skeletal parameters, especially valence angles [∠C5-C6-S = 121.19(6)°, ∠O=C6-C5 = 122.25(8)°, ∠C6-S-C2 = 106.80(4)°], differ from those typically found in acyclic thioester compounds, symptomatic of the presence of strain effects. The conventional ring strain energy was determined to be 7.5 kcal/mol at the MP2/6-311++G(d,p) level of calculation within the hyperhomodesmotic model approximation. Moreover, 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 9.35, 9.50, and 11.53 eV denote ionizations related with the n(S), n(O), and π(C=O) orbitals, respectively, demonstrating the importance of the -SC(O)- group in the outermost electronic properties.

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“…The opposite trend is true for open chair thioesters, where the C(sp 2 )S wavenumber appears at higher energies than the C(sp 3 )S value . Vibrational data for the β-propio-, , γ-butyro, and δ-valerothiolactones have already been reported. Relevant vibrational data for these thiolactone species are collected in Table .…”

Section: Results and Discussionmentioning

confidence: 97%

Conformational Transferability of the Sulfenyl Carbonyl Group −SC(O)– in Cyclic Thioesters

et al. 2013

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The molecular and crystal structure of two dithiolactones (formally dimers of ε-caprothiolactone and ω-hexadecathiolactone) have been determined by X-ray diffraction at low temperature, revealing that the thioester group is planar with a synperiplanar orientation of the C═O double bond with respect to the S-C single bond. This conformational behavior is in contrast to that found for the smaller cyclic members of this family, where the antiperiplanar conformation is enforced. It is hypothesized that strain effects play a major role for the energy balance in the conformational preference. In this context, the molecular, vibrational (infrared and Raman), and electronic properties of ε-caprothiolactone have also been analyzed by using a combined experimental, including gas-phase helium I photoelectron spectroscopy, and computational approach.

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Vibrational spectra of ?-thiopropiolactone

Cited by 4 publications

References 9 publications

Matrix Photochemistry, Photoelectron Spectroscopy, Solid-Phase Structure, and Ring Strain Energy of β-Propiothiolactone

Matrix Photochemistry, Photoelectron Spectroscopy, Solid-Phase Structure, and Ring Strain Energy of β-Propiothiolactone

Molecular and Electronic Structure of δ-Valerothiolactone

Conformational Transferability of the Sulfenyl Carbonyl Group −SC(O)– in Cyclic Thioesters

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