Gas phase structure and vibrational spectra of dimethoxysulfane (CH<sub>3</sub>O)<sub>2</sub>S

Baumeister, Edgar; Oberhammer, Heinz; Schmidt, Heinar; Steudel, Ralf

doi:10.1002/hc.520020605

Cited by 27 publications

(17 citation statements)

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“…Atoms of opposite charge approach each other, and the shortest intermolecular distance d (S ··· O) = 269.0 pm is in fair agreement with the experimental value of 282.4 pm 23. This non‐bonding distance is much longer than a corresponding single S–O bond as in dimethyl sulfoxylate MeO–S–OMe (162.5 pm33), for example, but shorter than the sum of the van der Waals radii (315 pm). Otherwise, the geometries of the two components SO 2 and H 2 O are rather undisturbed in the complex compared to the separate molecules.…”

Section: Resultssupporting

confidence: 79%

Sulfur Dioxide and Water: Structures and Energies of the Hydrated Species SO₂·nH₂O, [HSO₃]^–·nH₂O, [SO₃H]^–·nH₂O, and H₂SO₃·nH₂O (n = 0–8)

Steudel

2009

Eur J Inorg Chem

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The structures of a large number of hydrates of sulfur dioxide (SO2·nH2O), of the sulfonate ion ([HSO3]–·nH2O), of the tautomeric hydrogensulfite anion ([SO3H]–·nH2O), and of sulfurous acid (H2SO3·nH2O) with up to eight water molecules attached to these species have been optimized at the B3LYP/6‐31G(2df,p) level of theory (DFT). The calculated vibrational frequencies allow the definite assignment of certain characteristic modes, and in this way a convincing interpretation of published spectra of aqueous SO2 as well as of SO2 adsorbed on very cold ice crystals has been achieved for the first time. Single‐point calculations at the G3X(MP2) level of theory were used to calculate the binding energies of the water molecules in SO2·nH2O as well as the relative stabilities of the isomeric anionic species [HSO3]–·nH2O and [SO3H]–·nH2O. Generally, the water molecules tend to stick together forming clusters, whereas the particular sulfur‐containing molecule remains at the surface of the water cluster, but it is always strongly hydrogen‐bonded. Only when there are more than six water molecules are the anions more or less completely surrounded by water molecules. DFT calculations erroneously predict that the gaseous hydrated sulfonate ions are more stable than the isomeric hydrogensulfite ions, even when hydrated with six water molecules. However, if these hydrated species are calculated as being embedded in a polar continuum simulating the aqueous phase, the hydrogensulfite ions are more stable than the sulfonate ions, in agreement with various spectroscopic observations on aqueous sulfite solutions. On the other hand, at the higher G3X(MP2) level, the gaseous hydrated hydrogensulfite anions are more stable than the corresponding sulfonate ions only if the number of water molecules is larger than four, whereas for the weakly hydrated anions the order of relative energies is reversed. The possible implications of these results for the enzymatic oxidation of “sulfite ions” ([HSO3]– and [SO3H]–) by sulfite oxidase are discussed. The conversion of SO2·6H2O into its isomer H2SO3·5H2O is predicted to be exothermic (ΔH°298 = –56.1 kJ mol–1) and exergonic (ΔG°298 = –22.5 kJ mol–1). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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Section: Resultssupporting

confidence: 79%

Sulfur Dioxide and Water: Structures and Energies of the Hydrated Species SO₂·nH₂O, [HSO₃]^–·nH₂O, [SO₃H]^–·nH₂O, and H₂SO₃·nH₂O (n = 0–8)

Steudel

2009

Eur J Inorg Chem

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“…The formation of CF 3 OSOCH 3 can be ascertained by the occurrence of two pairs of IR bands at 994.3/917.5 and 757.1/739.4 cm –1 (Figure A), which are reasonably assigned to the characteristic stretching vibration modes ν(CH 3 –O)/ν(CF 3 –O) and ν sym (OSO)/ν asym (OSO), respectively. IR bands with similar frequencies have been found to the closely related CH 3 OSOCH 3 (ν in‑phase (CH 3 –O)/ν out‑of‑phase (CH 3 –O), 987/979 cm –1 , and ν sym (OSO), 731 cm –1 ), CF 3 SOCF 3 (ν(CF 3 –O), 937.5 cm –1 , and ν(S–O), 791.6 cm –1 ), and CF 3 OSF (ν(CF 3 –O), 934.1 cm –1 , and ν(S–O), 806.9 cm –1 ) . The IR bands for CF 3 OSOCH 3 in the range 1250–1100 cm –1 are heavily overlapped with those of CF 3 S(O)OCH 3 , which are mostly associated with the CF 3 stretching and CH 3 rocking modes.…”

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confidence: 59%

“…The former configuration is less favorable because of steric hindrance. The preference of the anti configuration has been experimentally established for CH 3 OSOCH 3 in both gas phase and solid state …”

Section: Results and Discussionmentioning

confidence: 99%

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Methoxysulfinyl Radical CH₃OSO: Gas-Phase Generation, Photochemistry, and Oxidation

Liu

et al. 2017

J. Phys. Chem. A

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Methylsulfoxide radicals CHSO (x = 1-4) are key reactive sulfur species (RSS) in the atmospheric oxidation of volatile organic sulfur compounds (VOSCs). Through flash vacuum pyrolysis (FVP) of trifluoromethanesulfinic acid methyl ester CFS(O)OCH at 1000 K, the methoxysulfinyl radical CHOSO has been generated in the gas phase and subsequently characterized in cryogenic N, Ar, and Ne matrices by IR spectroscopy. Upon 266 nm laser irradiation, CHOSO efficiently isomerizes to the less stable methylsulfonyl radical CHSO in matrices without noticeable decomposition. In the gas phase, CHOSO reacts with O and yields sulfinyl peroxyl radical CHOS(O)OO, a new member in the CHSO (x = 1-4) family. This radical dissociates into SO and CHO with the intermediacy of the sulfonyoxyl radical CHOSO under the 266 nm laser irradiation. Additionally, the photoisomerization of CFS(O)OCH to sulfenic ester CFOSOCH was also observed.

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“…The torsional angle C-O-S-0, however, seems to k slightly smaller in the solid (81.75O) than in the gas phase (84°) 6. In part c the positions of the C and H2 atoms have been projected into the plane; both atoms are slightly out of that plane.identical values in the gaseous and the solid state.…”

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confidence: 94%

Sulfur compounds. 158. Structure and electron density of solid dimethoxysulfane, (CH3O)2S

Buschmann¹,

Luger²,

Koritsánszky³

et al. 1992

J. Phys. Chem.

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9243(6) Liu, Y.; Zhang, Q. L.; Tittel, F. K.; Curl, R. F.; Smalley, R. E. J.(7) Ramen, M.; Heimbrook, C. A.; Schwartz, G. P.; Bondybey, V. E. (41) Hurley, M. M.; Pacia, L. F.; Christiansen, P. A.; Ross, R. B.; Ermler, W. C. J. Chem. Phys. 1986,84, 6840. LaJohn, L. A.; Christiansen, P. A,; Ross, R. B.; Atashroo, T.; Ermler, W. C. J. Chem. Phys. 1987, 87, 2812. Ross, R. B.; Powers, J. M.; Atashroo, T.; Ermler, W. C.; LaJohn, L. A.; Christiansen, P. A.High-resolution X-ray data were collected at a low temperature (1 10 (1) K) to determine the crystal and molecular structure and the deformation electron density (DED) of CH30SOCH3. Crystal data: a = 9.156 (S), b = 7.451 (6), c = 6.593 (3) A, Pbcn (centric), Z = 4. The molecules are in special positions of C2 symmetry with bond lengths SO = 1.6212 (7), CO = 1.4444 (6), and CH = 1.067 (7) A (av), bond angles OS0 = 104.78 (5)", COS = 115.76 (2)O, OCH = 108.3O (av), and torsional angle COS0 = 81.75 ( 2 ) ' . The OCH, units deviate considerably from C3, symmetry. The deformation electron density is analyzed in terms of static (SDD) and dynamic deformation density (DDD) calculated from the fitted multipolepopulations and X-X Fourier synthesis. The r lone pairs at S and 0 are clearly discernible in these maps but there is no indication of any anomeric effect. The torsional angle of 82O at the S-0 bonds must therefore be the result of the lone pair interaction only. The molecules form layers with the OS0 units in parallel planes and the methyl groups separating these planes from each other. There are no intermolecular contacts shorter than the van der Waals distances, but the sulfur atoms are coordinated by two nonbonded oxygen atoms of neighboring molecules from the same plane resulting in a 2 + 2 coordination of local symmetry C, .

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Gas phase structure and vibrational spectra of dimethoxysulfane (CH₃O)₂S

Abstract: The vapor phase structure of ( C H 3 0 )

Cited by 27 publications

References 28 publications

Sulfur Dioxide and Water: Structures and Energies of the Hydrated Species SO₂·nH₂O, [HSO₃]^–·nH₂O, [SO₃H]^–·nH₂O, and H₂SO₃·nH₂O (n = 0–8)

Sulfur Dioxide and Water: Structures and Energies of the Hydrated Species SO₂·nH₂O, [HSO₃]^–·nH₂O, [SO₃H]^–·nH₂O, and H₂SO₃·nH₂O (n = 0–8)

Methoxysulfinyl Radical CH₃OSO: Gas-Phase Generation, Photochemistry, and Oxidation

Sulfur compounds. 158. Structure and electron density of solid dimethoxysulfane, (CH3O)2S

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Gas phase structure and vibrational spectra of dimethoxysulfane (CH3O)2S

Abstract: The vapor phase structure of ( C H 3 0 )

Cited by 27 publications

References 28 publications

Sulfur Dioxide and Water: Structures and Energies of the Hydrated Species SO2·nH2O, [HSO3]–·nH2O, [SO3H]–·nH2O, and H2SO3·nH2O (n = 0–8)

Sulfur Dioxide and Water: Structures and Energies of the Hydrated Species SO2·nH2O, [HSO3]–·nH2O, [SO3H]–·nH2O, and H2SO3·nH2O (n = 0–8)

Methoxysulfinyl Radical CH3OSO: Gas-Phase Generation, Photochemistry, and Oxidation

Sulfur compounds. 158. Structure and electron density of solid dimethoxysulfane, (CH3O)2S

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Gas phase structure and vibrational spectra of dimethoxysulfane (CH₃O)₂S

Sulfur Dioxide and Water: Structures and Energies of the Hydrated Species SO₂·nH₂O, [HSO₃]^–·nH₂O, [SO₃H]^–·nH₂O, and H₂SO₃·nH₂O (n = 0–8)

Sulfur Dioxide and Water: Structures and Energies of the Hydrated Species SO₂·nH₂O, [HSO₃]^–·nH₂O, [SO₃H]^–·nH₂O, and H₂SO₃·nH₂O (n = 0–8)

Methoxysulfinyl Radical CH₃OSO: Gas-Phase Generation, Photochemistry, and Oxidation