Correlation of the rates of solvolysis of arylmethyl p-toluenesulfonates: application of the aromatic ring parameter and a discussion of similarity models

Article Abstract:

Rates of arylmethyl p-toluenesulfonates solvolysis have been correlated with application of the aromatic ring parameter through use of the scales N-sub-T and Y-sub-OTs in the extended Grunwald-Winstein equation. Similarity models are relevant. A third term controled by the aromatic ring parameter shows the extra term is statistically significant. Sensitivities to changes in solvent nucleophilicity go up as more electron-withdrawing substituents are added; sensitivities to changes in ionizing power and changes in the aromatic ring parameter go down at the same time as the other sensitivities go up.

Reactivity (Chemistry), Aromatic compounds, Solvents

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The preparation, X-ray crystal structure, and spectroscopic characterization of pentafluoro-phenyl-bis(pentafluorophenylthio)sulfonium hexafluoroarsenate, ((C6F5S)2SC6F5)(AsF6)

Article Abstract:

Pentafluorophenyl-bis(pentafluorophenylthio)sulfonium hexafluoroarsenate or ((C6F5S)2SC6F5)(AsF6) has been prepared by reacting AsF5 with (C6F5)2S2 in SO2, liquid, at ambient temperature. Then it was studied through use of powder and single-crystal X-ray diffraction and both FT-Raman and IR spectroscopy. It appears that ((CH3)2ClS3)+ has a structure with sulfur-sulfur distances that are identical and that the structure is therefore likely as written, not ((CH3)2SSSCl)+, which had been reported in the past.

Arsenic compounds, Organometallic chemistry, Fluorocarbons

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