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Arylcarbonium ions in solution Gatzke, Arnold L.

Abstract

Various aspects of the chemistry of carbonium ions have been investigated and are reported herein. A preliminary study of the behavior of 1,1-di-anisylethylene and 1,1-diphenylethylene in formic acid was made to determine whether reduction of the intermediate carbonium ion occurs or whether the alleged π complex is formed. 1,1-Diphenylethylene was found to be completely unreactive towards formic acid under the conditions used. 1,1-Di-p-anisylethylene did not undergo any observable reduction but showed the presence of an absorption band in the 600 mu. range. Evidence is presented which suggests this band is due to formation of the species which has been called a π complex. The effect of ∝ deuteration of benzhydrol on the following equilibrium was measured using a spectrophotometry method. The results obtained showed an ∝deut- Ph₂CHOH+H₂SO₄ ⇌(symbol omitted) Ph₂C⁺H+HSO₄⁻ + H₂O erium isotope effect of KH/KD = 1.29±.05. The theoritical interpretation of the cause of this effect is discussed. An investigation into the nature of the colourless species present in solution when triarylmethyl perchlorates are dissolved in chloroform and acetone, showed that when chloroform is the solvent the colourless species is the triarylcarbinol, which result from the presence of small amounts of water in the solvent. In the case of acetone as the solvent, a positive identification of the colourless species could not be made. The U.V. absorption spectra of tri-p-anisyl-, tri-p-tolyl- and triphenylcarbinol were determined in various concentrations of sulphuric acid. Three different spectra are observed for each carbinol in the 400-500 mu. range, a spectrum due to the normal carbonium ion, another to a sulphonated carbonium ion and a third due to an interaction of the normal carbonium ion with the solvent. These spectra can qualitatively account for some of the anomalous spectra reported in the literature.

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