Journal of Organic & Inorganic Chemistry

Chloronium cations and carbocations in condensed phases: stabilization and properties

2^nd Edition of EuroSciCon Conference on Chemistry
February 19-20, 2019 | Prague, Czech Republic

Evgenii S Stoyanov

N N Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, Russia Novosibirsk State University, Russia

Posters & Accepted Abstracts: J Org Inorg Chem

DOI: 10.21767/2472-1123-C1-021

Abstract

The simple chloronium salts with exceptionally stable carborane anion, R2Cl+ (CHB11Cl₁₁¯), with R=CH₃ (see Figure), C₂H₅ and (CH₃)₂CH are stable at room temperature and serve as intermediates in obtaining different carbocations. Some chemical properties of chloronium ions in dichloroethane solutions and in the solid salts at room and elevated temperatures (up to 150°C) are reported. Decomposition of chloronium salts resulted in the formation of the high purity carbocation salts. Their detailed IR spectra showed a strong discrepancy with the generally accepted theory of hyperconjugative stabilization of saturated carbocations, based on the modern ab initio calculations. We proposed a refined theory that allowed us to interpret the IR spectra of all carbocations having sp² carbon atom in gaseous, liquid, and solid phases. It was proved that CH₃/CH₂ groups of carbocations, which are involved in hyperconjugation, show the stretch and band vibration typical for those of corresponding groups of the neutral alkanes (that is retain their isoelectronic nature) in IR spectra. Hyperconjugation and polarization are equally important and closely linked in stabilization of carbocations: the strengthening of one effect weakens the second and vice versa. We obtained the salts of unsaturated chloronium cations and unsaturated carbocations with conjugated multiple CC bonds, which are stable at ambient conditions for the first time.

Biography

E-mail:

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