Abstract: Chloronium cations in their salts (CnH2n+1)(2)Cl+{CHB11,Cl-11}, 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 degrees 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)(2)Cl+ ]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)(2)F+(CHB11F11-) must exist at low temperatures. The proposed (CH3)(2)F+ cation is much more reactive than-the corresponding chloronium showing at room temperature chemical properties expected of (CH3)(2)Cl+ at elevated temperatures.

Cite: Stoyanov E.S.
Chemical Properties of Dialkyl Halonium Ions (R(2)Hal(+)) and Their Neutral Analogues, Methyl Carboranes, CH3-(CHB(11)Hal(11)) Where Hal = F, Cl
Journal of Physical Chemistry A. 2017. V.121. N15. P.2918-2923. DOI: 10.1021/acs.jpca.7b01203 WOS Scopus РИНЦ

Dates:

Published online:	Apr 6, 2017
Published print:	Apr 20, 2017

Identifiers:

Web of science	WOS:000400039000008
Scopus	2-s2.0-85020030045
Elibrary	31027999
OpenAlex	W2599527586

Altmetrics: