В журнале International Journal of Molecular Sciences (IF=6,208) опубликована статья с участием сотрудников Института: д.х.н. Е.С. Стоянова (внс, ЛМР) и И.В. Стояновой (инженер ЛМР):
The Chloronium Cation [(C2H3)2Cl+] and Unsaturated C4-Carbocations with C=C and C≡C Bonds in Their Solid Salts and in Solutions: An H1/C13 NMR and Infrared Spectroscopic Study
Evgenii S. Stoyanov and Irina V. Stoyanova
Int. J. Mol. Sci. 2022, 23(16), 9111;
Publication Date: Mayr 1, 2022
https://doi.org/10.3390/ijms23169111
(This article belongs to the Special Issue Structure, Energy and Dynamics of Molecular Interactions)
Abstract
Solid salts of the divinyl chloronium (C2H3)2Cl+ cation (I) and unsaturated C4H6Cl+ and C4H7+ carbocations with the highly stable CHB11Hal11− anion (Hal=F, Cl) were obtained for the first time. At 120 °C, the salt of the chloronium cation decomposes, yielding a salt of the C4H5+ cation. This thermally stable (up to 200 °C) carbocation is methyl propargyl, CH≡C-C+-H-CH3 (VI), which, according to quantum chemical calculations, should be energetically much less favorable than other isomers of the C4H7+ cations. Cation VI readily attaches HCl to the formal triple C≡C bond to form the CHCl=CH-C+H-CH3 cation (VII). In infrared spectra of cations I, VI, and VII, frequencies of C=C and C≡C stretches are significantly lower than those predicted by calculations (by 400–500 cm−1). Infrared and 1H/13C magic-angle spinning NMR spectra of solid salts of cations I and VI and high-resolution 1H/13C NMR spectra of VII in solution in SO2ClF were interpreted. On the basis of the spectroscopic data, the charge and electron density distribution in the cations are discussed. View Full-Text
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