Infrared Absorption Spectra of SSO<sup>-</sup> Anion in Solid Argon

Zeng, A.; Lei, Yu; Wang, Yun; Kong, Qingyu; Xu, Qiang; Zhou, Mingfei

doi:10.1021/jp0485800

Cited by 16 publications

(15 citation statements)

References 38 publications

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“…Indeed, most of the standard computational methods and basis sets have been shown to be unable to properly treat this moiety, leading to considerable discrepancies between the experimental and theoretically predicted values for the S@O bond lengths and for the vibrational frequencies associated with this bond [22][23][24][25]. The underestimation of the theoretically predicted frequencies for the S@O stretching vibrations was noticed previously for different types of compounds containing the S@O bond, from simple molecules, as dimethyl sulfate [26], dimethyl sulfite [27] or the SSO À anion [28], to more complex species, like 5-methyl-1H,3H-pyrrolo [1,2c] [1,3]thiazole-6,7-dicarboxylate 2,2-dioxide [29]. Although a good agreement of the experimental and predicted frequencies was achieved for both dimethyl sulfate and sulfite when the B3LYP method was used together with the split valence quadruple-f basis set (aug-cc-pVQZ) [26,27], calculations on pseudosaccharins at this level of theory are currently unpractical due to its excessive computational cost.…”

Section: Introductionmentioning

confidence: 92%

Molecular structure and infrared spectra of the monomeric 3-(methoxy)-1,2-benzisothiazole 1,1-dioxide (methyl pseudosaccharyl ether)

Kaczor

Almeida

Gómez‐Zavaglia

et al. 2008

Journal of Molecular Structure

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The computational description of saccharin (1,2-benzisothiazol-3(2H)-one-1,1-dioxide) and its derivatives is difficult due to the presence of hypervalent S@O bonds in their structures. Therefore, in this investigation, the HF, DFT/B3LYP and MP2 methods were used to predict the geometry and the infrared spectrum of the saccharyl derivative 3-(methoxy)-1,2-benzisothiazole 1,1-dioxide (MBID). Their relative predictive capabilities were then evaluated by comparing the obtained results with experimentally available data, namely the newly obtained IR spectra of MBID isolated in low-temperature inert matrices. For each method, different basis sets [6-31++G(d,p), 6-31++G(3df,3pd), 6-311++G(d,p), 6-311++G(2df,2pd), 6-311++G(3df,3pd), aug-cc-pVDZ and aug-cc-pVTZ] were considered. The best overall agreement has been achieved at the B3LYP/6-311++G(3df,3pd) and B3LYP/6-31++G(3df,3pd) levels of theory, showing the adequacy of the B3LYP functional to describe the investigated properties in this type of compounds and stressing the relevance of including high-order polarization functions in the basis set.The chosen level of theory 3pd)] was applied to analyze the vibrational spectra and the geometry of the title molecule. In agreement with the experiment, the CAOAC linkage in MBID is predicted by these calculations to exhibit considerably short (1.320 Å ) and long (1.442 Å ) (N@)CAO and (H 3 )CAO bonds, respectively, and a hybridization of the central oxygen atom close to sp 2 (the CAOAC angle is predicted to be ca. 117°). This CAOAC bonding pattern fits the well-known high reactivity of MBID upon thermal rearrangement, which has been shown to result in easy selective [1,3 0 ]-isomerization of the compound.

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Section: Introductionmentioning

confidence: 92%

Molecular structure and infrared spectra of the monomeric 3-(methoxy)-1,2-benzisothiazole 1,1-dioxide (methyl pseudosaccharyl ether)

Kaczor

Almeida

Gómez‐Zavaglia

et al. 2008

Journal of Molecular Structure

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“…However, it was found that this is not the case for molecules with SO bonds, where the theory often yields frequencies that underestimate the experimentally observed ones. This behavior has been found even for molecules as simple as SSO [10]. Besides, it is also well known that the accumulated knowledge on the molecular structures, conformational and spectroscopic properties, and chemical reactivity in general, of sulfur compounds is still incipient when compared, for instance, with that of their oxygen analogue compounds.…”

Section: Introductionmentioning

confidence: 94%

Matrix-isolation FT-IR spectra and theoretical study of dimethyl sulfate

Borba¹,

Gómez‐Zavaglia²,

Simões³

et al. 2005

Spectrochimica Acta Part A: Molecular and Biomolecular Spectros

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The preferred conformations of dimethyl sulfate and their vibrational spectra were studied by matrix-isolation FT-IR spectroscopy and theoretical methods (DFT and MP2, with basis sets of different sizes, including the quadruple-zeta, aug-cc-pVQZ basis). Conformer GG (of C2 symmetry and exhibiting OSOC dihedral angles of 74.3 degrees ) was found to be the most stable conformer in both the gaseous phase and isolated in argon. Upon annealing of the matrix, the less stable observed conformer (GT; with C1 symmetry) quickly converts to the GG conformer, with the resulting species being embedded in a matrix-cage which corresponds to the most stable matrix-site for GG form. The highest energy TT conformer, which was assumed to be the most stable conformer in previous studies, is predicted by the calculations to have a relative energy of ca. 10 kJ mol-1 and was not observed in the spectra of the matrix-isolated compound.

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“…According to previous analyses, [12][13][14] the vibrational frequencies associated with SdO bond stretches are usually underestimated when calculated both at the DFT (B3LYP) level with the split-valence triple-6-311++G(d,p) basis set and at the MP2 level with the split-valence double-6-31++G(d,p) basis set. This result does not follow the usual trend, which is a general overestimation of vibrational frequencies by this type of calculations.…”

Section: Methodsmentioning

confidence: 96%

Conformational Behavior of Dimethyl 5-Methyl-1H,3H-pyrrolo[1,2-c][1,3]thiazole-6,7-dicarboxylate 2,2-Dioxide Isolated in Low-Temperature Matrixes

et al. 2006

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The structure of dimethyl 5-methyl-1H,3H-pyrrolo[1,2-c][1,3]thiazole-6,7-dicarboxylate 2,2-dioxide (PTD) was investigated in low-temperature noble gas matrixes (Ar, Kr, Xe), amorphous solid, and the crystalline state by infrared spectroscopy and computational methods. The geometry of PTD conformers is defined by the orientation of two methyl ester groups, which may adopt pseudo-trans or pseudo-cis positions in relation to the pyrrolo-thiazole system. For both methyl ester groups, the latter arrangement was predicted by the calculations to be energetically the most favorable in the isolated molecule. The envelope form of the thiazolidine ring is present in all conformers, with the sulfur atom placed in the apex position, while the pyrrole ring is almost planar. Three types of conformers differing in the orientation of the methyl ester groups relative to the pyrrolo-thiazole system (cis/cis, trans/cis, cis/trans) were identified in the matrixes. The cis/cis forms were found to be the most stable ones in both gaseous state and argon matrixes. On the other hand, the more polar trans/cis forms were found to be stabilized in the more polarizable krypton and xenon matrixes as well as in the neat amorphous and crystalline phases. On the basis of annealing experiments, performed in argon and xenon matrixes up to 35 and 68 K, respectively, conformational changes preceding the aggregation of the compound are suggested.

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Infrared Absorption Spectra of SSO^- Anion in Solid Argon

Cited by 16 publications

References 38 publications

Molecular structure and infrared spectra of the monomeric 3-(methoxy)-1,2-benzisothiazole 1,1-dioxide (methyl pseudosaccharyl ether)

Molecular structure and infrared spectra of the monomeric 3-(methoxy)-1,2-benzisothiazole 1,1-dioxide (methyl pseudosaccharyl ether)

Matrix-isolation FT-IR spectra and theoretical study of dimethyl sulfate

Conformational Behavior of Dimethyl 5-Methyl-1H,3H-pyrrolo[1,2-c][1,3]thiazole-6,7-dicarboxylate 2,2-Dioxide Isolated in Low-Temperature Matrixes

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Infrared Absorption Spectra of SSO- Anion in Solid Argon

Cited by 16 publications

References 38 publications

Molecular structure and infrared spectra of the monomeric 3-(methoxy)-1,2-benzisothiazole 1,1-dioxide (methyl pseudosaccharyl ether)

Molecular structure and infrared spectra of the monomeric 3-(methoxy)-1,2-benzisothiazole 1,1-dioxide (methyl pseudosaccharyl ether)

Matrix-isolation FT-IR spectra and theoretical study of dimethyl sulfate

Conformational Behavior of Dimethyl 5-Methyl-1H,3H-pyrrolo[1,2-c][1,3]thiazole-6,7-dicarboxylate 2,2-Dioxide Isolated in Low-Temperature Matrixes

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Infrared Absorption Spectra of SSO^- Anion in Solid Argon