Stoyanov, E.S.; Bagryanskaya, I.Y.; Stoyanova, I.V. Substitution of H Atoms in Unsaturated (Vinyl-Type) Carbocations by Cl or O Atoms. Int. J. Mol. Sci.2023, 24, 10734.
Stoyanov, E.S.; Bagryanskaya, I.Y.; Stoyanova, I.V. Substitution of H Atoms in Unsaturated (Vinyl-Type) Carbocations by Cl or O Atoms. Int. J. Mol. Sci. 2023, 24, 10734.
Stoyanov, E.S.; Bagryanskaya, I.Y.; Stoyanova, I.V. Substitution of H Atoms in Unsaturated (Vinyl-Type) Carbocations by Cl or O Atoms. Int. J. Mol. Sci.2023, 24, 10734.
Stoyanov, E.S.; Bagryanskaya, I.Y.; Stoyanova, I.V. Substitution of H Atoms in Unsaturated (Vinyl-Type) Carbocations by Cl or O Atoms. Int. J. Mol. Sci. 2023, 24, 10734.
Abstract
Introduction of Cl- and O- atoms into C4-vinyl carbocations was studied by X-ray diffraction analysis and IR spectroscopy. Chlorine atoms are weak electron acceptors in ordinary molecules, but within vinyl carbocations, manifest themselves as strong electron donors that accept a positive charge. The attachment of a Cl atom directly to a C=C bond leads to an increase in the e-density on it, exceeding that of the common double bond. The positive charge should be concentrated on the Cl atom, and weak δ- may appear on the C=C bond. More distant attachment of the Cl atom—to a C atom adjacent to the C=C bond—has a weaker effect on it. If two Cl atoms are attached to the Сγ atom of the vinyl cation, as in Cl2СγСδHСαHCH3, then the cation switches to the allyl type with two practically equivalent and almost uncharged СγСδСα bonds. When such a strong nucleophile as the O atom is introduced into the carbocation, a protonated ester molecule with a C-O(H+)-C group and a C=C bond forms. Nonetheless, in the future, there is still a possibility of obtaining carbocations with a non-protonated C-O-C group.
Keywords
vinyl carbocations; carborane salts; IR spectroscopy
Subject
Chemistry and Materials Science, Organic Chemistry
Copyright:
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