Vibrational Spectra of Sulphonyl Derivatives. V. A Reassignment of the SO2 Stretching Frequencies in Sulphonyl Fluorides

Ham, NS; Hambly, AN; Laby, R. H.

doi:10.1071/ch9600443

Cited by 39 publications

(4 citation statements)

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“…Evidence for electronic coupling between the [Fe4X4]2+ core and the thiophenolate ligand is brought forth by the resonant enhancement of the 698-and 1088-cm"1 bands of the latter compared to their homologues in non resonant Raman spectra of the free thiol, taking its 1000-and 1026-cm"1 bands as internal standards (Figure 3C). The 698and 1088-cm"1 bands of [Fe4X4(SPh)4]2" can be attributed to (C2o) modes of the thiophenolate ligand involving some C-S stretching character (Ham et al, 1960;Scott et al, 1956). The "Peak height of the totally symmetric (A,) Fe-S, stretching mode at ca.…”

Section: Discussionmentioning

confidence: 99%

[4Fe-4X]2+ (X = sulfur, selenium) clusters in Clostridium pasteurianum ferredoxin and in synthetic analogs: structural data from resonance Raman spectroscopy

Moulis¹,

Meyer²,

Lutz³

1984

Biochemistry

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Section: Discussionmentioning

confidence: 99%

[4Fe-4X]2+ (X = sulfur, selenium) clusters in Clostridium pasteurianum ferredoxin and in synthetic analogs: structural data from resonance Raman spectroscopy

Moulis¹,

Meyer²,

Lutz³

1984

Biochemistry

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“…In this and all other cases the presence of the sulfonyl fluoride was confirmed by ir and fluorine nmr. 37 The absence of sulfonyl chloride was checked by testing with silver nitrate and ammonium thiocyanate.38 4-Fluorobenzenesulfonyl Fluoride. 4-Fluorobenzenesulfonyl chloride (5 g, 0.026 mol; Aldrich, mp 33-35°) was converted to the sulfonyl fluoride by the method of Sigler, et al 39 The liquid product (0.015 mol) was distilled at 133-136°( ca.…”

Section: Methodsmentioning

confidence: 99%

Kinetics of inactivation of .alpha.-chymotrypsin with substituted benzenesulfonyl fluorides

Gerig¹,

Roe²

1974

J. Am. Chem. Soc.

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The dissociation constants for complexes of chymotrypsin Aa with a series of (V-acyl-and A-peptidyl-2phenylethylamine competitive inhibitors were measured in a 9.5 % ethanol, 0.10 M CaCls solution at pH 7.80 at 25°. Individual subsite binding free energies for the extended substrate binding site in chymotrypsin were calculated. The free energies of binding in this series of vV-acyl-and A-peptidyl-2-phenylethylamines become more negative with increasing number of interactions with enzyme as predicted from the crystallographic model. The major contributors to the binding free energy are hydrophobic interactions, the Si-Pi tosyl pocket-phenylethyl group interaction(2 kcal/mol) and the interaction of an aliphatic side chain of a P2 residue with Ile-99 in the S2 binding subsite of the enzyme. The individual subsite binding free energies are not additive. Comparison of the dissociation constants of Á-acyl-and X-peptidyl-2-phenylethylamines with the Xm values for the corresponding substrates indicates that the inhibitors are more tightly bound. This is consistent with the hypothesis that serine proteases place the scissionable peptide bond of a substrate on a stereoelectronic "rack" favoring formation of a tetrahedral intermediate. RecentX-ray studies on chymotrypsin A7 crystals .

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“…The experimental Raman spectra of liquid 4-TsN 3 were recorded from 50 to 3200 cm –1 at ambient conditions as shown in Figure a. As the vibrational modes of the same groups have similar characteristic frequencies in different compounds, the vibrations of methyl, phenyl, sulfonyl, and azide groups were analyzed on the basis of the literature data of toluene, benzenesulfonyl, sulfonyl azide, and organic azide. − For further assignment, the vibrational property of 4-TsN 3 was calculated using the DFT method, and the calculated Raman spectra of 4-TsN 3 are presented in Figure b. The observed and calculated Raman bands corresponding to the assigned vibrational modes are summarized in Table .…”

Section: Results and Discussionmentioning

confidence: 99%

Effect of Pressure on 4-Toluenesulfonyl Azide Studied by Raman Scattering and Synchrotron X-ray Diffraction

Jiang

Zhu

et al. 2017

J. Phys. Chem. C

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The effect of high pressure on the phase transition behaviors of 4-toluenesulfonyl azide (C7H7N3O2S, 4-TsN3) have been investigated by Raman scattering and angle-dispersive X-ray diffraction (ADXRD) measurements in diamond anvil cells up to ∼15.6 GPa at room temperature. The liquid 4-TsN3 (phase I) begins to transform into solid state (phase II) at 0.7 GPa, and turns to phase III at about 2.7 GPa, then going to phase IV at about 6.3 GPa. The phase IV of 4-TsN3 finally starts to turn into an amorphous state above 10.6 GPa. The first phase transition (phase I to phase II) of 4-TsN3 is triggered by the rearrangement of CH···π interaction, and the second phase transition (phase II to phase III) is attributed to the conformational change, then the rotation of sulfonyl leads to the third phase transition (phase III to phase IV). The variation of sulfonyl has an influence on the behavior of azide group which will bend and further decompose upon compression. In the process of amorphization, the lattice structure of 4-TsN3 abnormally expanded, which may be caused by the change of CH···π interactions. We anticipate that the high pressure study of 4-TsN3 provides information toward further understanding and optimizing synthesis conditions of the polymeric nitrogen using azides as starting materials, especially using organic azides.

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Vibrational Spectra of Sulphonyl Derivatives. V. A Reassignment of the SO2 Stretching Frequencies in Sulphonyl Fluorides

Cited by 39 publications

References 0 publications

[4Fe-4X]2+ (X = sulfur, selenium) clusters in Clostridium pasteurianum ferredoxin and in synthetic analogs: structural data from resonance Raman spectroscopy

[4Fe-4X]2+ (X = sulfur, selenium) clusters in Clostridium pasteurianum ferredoxin and in synthetic analogs: structural data from resonance Raman spectroscopy

Kinetics of inactivation of .alpha.-chymotrypsin with substituted benzenesulfonyl fluorides

Effect of Pressure on 4-Toluenesulfonyl Azide Studied by Raman Scattering and Synchrotron X-ray Diffraction

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