Chemical Properties of Dialkyl Halonium Ions (R2Hal+) and Their Neutral Analogues, Methyl Carboranes, CH3-(CHB11Hal11), Where Hal = F, Cl

Evgenii S. Stoyanov

Research output: Contribution to journalArticlepeer-review

4 Citations (Scopus)

Abstract

Chloronium cations in their salts (CnH2n+1)2Cl+{CHB11Cl11 -}, with n = 1 to 3 and exceptionally stable carborane anions, are stable at ambient and elevated temperatures. The temperature at which they decompose to carbocations with HCl elimination (below 150 °C) decreases with the increasing n from 1 to 3 because of increasing ionicity of C-Cl bonds in the C-Cl+-C bridge. At room temperature, the salts of cations with n ≥ 4 [starting from t-Bu2Cl+ or (cyclo-C5H11)2Cl+] are unstable and decompose. With decreasing chloronium ion stability, their ability to interact with chloroalkanes to form oligomeric cations increases. It was shown indirectly that unstable salt of fluoronium ions (CH3)2F+(CHB11F11 -) must exist at low temperatures. The proposed (CH3)2F+ cation is much more reactive than the corresponding chloronium, showing at room temperature chemical properties expected of (CH3)2Cl+ at elevated temperatures.

Original languageEnglish
Pages (from-to)2918-2923
Number of pages6
JournalJournal of Physical Chemistry A
Volume121
Issue number15
DOIs
Publication statusPublished - 20 Apr 2017

Keywords

  • FLUORONIUM ION
  • HYPERCONJUGATION
  • CARBOCATIONS
  • TEMPERATURE
  • PROTONATION
  • ENERGETICS
  • EXCHANGE
  • CATIONS
  • ACIDITY
  • HALIDES

Fingerprint Dive into the research topics of 'Chemical Properties of Dialkyl Halonium Ions (R<sub>2</sub>Hal<sup>+</sup>) and Their Neutral Analogues, Methyl Carboranes, CH<sub>3</sub>-(CHB<sub>11</sub>Hal<sub>11</sub>), Where Hal = F, Cl'. Together they form a unique fingerprint.

Cite this