Substitution of H Atoms in Unsaturated (Vinyl-Type) Carbocations by Cl or O Atoms

Introduction of Cl and O atoms into C -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 a...

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Bibliographic Details
Published in:International journal of molecular sciences 2023-06, Vol.24 (13), p.10734
Main Authors: Stoyanov, Evgenii S, Bagryanskaya, Irina Yu, Stoyanova, Irina V
Format: Article
Language:English
Subjects:
Acetylene
Carbon
carborane salts
Cations
Cations - chemistry
Chlorine
Chlorine - chemistry
Crystals
Infrared spectroscopy
Ions
IR spectroscopy
Olefins
Spectrum analysis
vinyl carbocations
X-ray diffraction
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Summary:Introduction of Cl and O atoms into C -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, e.g., to a C atom adjacent to the C=C bond, has a weaker effect on it. If two Cl atoms are attached to the C atom of the vinyl cation, as in Cl C C HC HCH , then the cation switches to the allyl type with two practically equivalent and almost uncharged C C C 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.
ISSN:1422-0067
1661-6596
1422-0067
DOI:10.3390/ijms241310734