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Stabilization of carbocations CH3+, C2H5+, i-C3H7+, tert-Bu+, and cyclo-pentyl+ in solid phases : Experimental data versus calculations. / Stoyanov, Evgenii S.; Nizovtsev, Anton S.

In: Physical Chemistry Chemical Physics, Vol. 19, No. 10, 08.03.2017, p. 7270-7279.

Research output: Contribution to journal › Article › peer-review

Harvard

Stoyanov, ES & Nizovtsev, AS 2017, 'Stabilization of carbocations CH3+, C2H5+, i-C3H7+, tert-Bu+, and cyclo-pentyl+ in solid phases: Experimental data versus calculations', Physical Chemistry Chemical Physics, vol. 19, no. 10, pp. 7270-7279. https://doi.org/10.1039/c6cp06839a

APA

Stoyanov, E. S., & Nizovtsev, A. S. (2017). Stabilization of carbocations CH3+, C2H5+, i-C3H7+, tert-Bu+, and cyclo-pentyl+ in solid phases: Experimental data versus calculations. Physical Chemistry Chemical Physics, 19(10), 7270-7279. https://doi.org/10.1039/c6cp06839a

Vancouver

Stoyanov ES, Nizovtsev AS. Stabilization of carbocations CH3+, C2H5+, i-C3H7+, tert-Bu+, and cyclo-pentyl+ in solid phases: Experimental data versus calculations. Physical Chemistry Chemical Physics. 2017 Mar 8;19(10):7270-7279. doi: 10.1039/c6cp06839a

Author

Stoyanov, Evgenii S. ; Nizovtsev, Anton S. / Stabilization of carbocations CH3+, C2H5+, i-C3H7+, tert-Bu+, and cyclo-pentyl+ in solid phases : Experimental data versus calculations. In: Physical Chemistry Chemical Physics. 2017 ; Vol. 19, No. 10. pp. 7270-7279.

BibTeX

@article{d6b7e3c15ae8478d87e25488fbace03b,
title = "Stabilization of carbocations CH3+, C2H5+, i-C3H7+, tert-Bu+, and cyclo-pentyl+ in solid phases: Experimental data versus calculations",
abstract = "Comparison of experimental infrared (IR) spectra of the simplest carbocations (with the weakest carborane counterions in terms of basicity, CHB11Hal11-, Hal = F, Cl) with their calculated IR spectra revealed that they are completely inconsistent, as previously reported for the t-Bu+ cation [Stoyanov E. S., et al. J. Phys. Chem. A, 2015, 119, 8619]. This means that the generally accepted explanation of hyperconjugative stabilization of the carbocations should be revised. According to the theory, one CH bond (denoted as CHClubsuit sign) from each CH3/CH2 group transfers its σ-electron density to the empty 2pz orbital of the sp2 C atom, whereas the σ-electron density on the other CH bonds of the CH3/CH2 group slightly increases. From experimental IR spectra it follows that donation of the σ-electrons from the CHClubsuit sign bond to the 2pz C-orbital is accompanied by equal withdrawal of the electron density from other CH bonds, that is, the electrons are supplied from each CH bond of the CH3/CH2 group. As a result, all CH stretches of the group are red shifted, and IR spectra show typical CH3/CH2 group vibrations. Experimental findings provided another clue to the electron distribution in the hydrocarbon cations and showed that the standard computational techniques do not allow researchers to explain a number of recently established features of the molecular state of hydrocarbon cations.",
keywords = "STABLE CARBONIUM-IONS, BUTYL CATION, CONDENSED PHASES, HYPERCONJUGATION, PROTONATION, ENERGETICS, CHEMISTRY",
author = "Stoyanov, {Evgenii S.} and Nizovtsev, {Anton S.}",
note = "Publisher Copyright: {\textcopyright} the Owner Societies 2017.",
year = "2017",
month = mar,
day = "8",
doi = "10.1039/c6cp06839a",
language = "English",
volume = "19",
pages = "7270--7279",
journal = "Physical Chemistry Chemical Physics",
issn = "1463-9076",
publisher = "Royal Society of Chemistry",
number = "10",

}

RIS

TY - JOUR

T1 - Stabilization of carbocations CH3+, C2H5+, i-C3H7+, tert-Bu+, and cyclo-pentyl+ in solid phases

T2 - Experimental data versus calculations

AU - Stoyanov, Evgenii S.

AU - Nizovtsev, Anton S.

N1 - Publisher Copyright: © the Owner Societies 2017.

PY - 2017/3/8

Y1 - 2017/3/8

N2 - Comparison of experimental infrared (IR) spectra of the simplest carbocations (with the weakest carborane counterions in terms of basicity, CHB11Hal11-, Hal = F, Cl) with their calculated IR spectra revealed that they are completely inconsistent, as previously reported for the t-Bu+ cation [Stoyanov E. S., et al. J. Phys. Chem. A, 2015, 119, 8619]. This means that the generally accepted explanation of hyperconjugative stabilization of the carbocations should be revised. According to the theory, one CH bond (denoted as CHClubsuit sign) from each CH3/CH2 group transfers its σ-electron density to the empty 2pz orbital of the sp2 C atom, whereas the σ-electron density on the other CH bonds of the CH3/CH2 group slightly increases. From experimental IR spectra it follows that donation of the σ-electrons from the CHClubsuit sign bond to the 2pz C-orbital is accompanied by equal withdrawal of the electron density from other CH bonds, that is, the electrons are supplied from each CH bond of the CH3/CH2 group. As a result, all CH stretches of the group are red shifted, and IR spectra show typical CH3/CH2 group vibrations. Experimental findings provided another clue to the electron distribution in the hydrocarbon cations and showed that the standard computational techniques do not allow researchers to explain a number of recently established features of the molecular state of hydrocarbon cations.

AB - Comparison of experimental infrared (IR) spectra of the simplest carbocations (with the weakest carborane counterions in terms of basicity, CHB11Hal11-, Hal = F, Cl) with their calculated IR spectra revealed that they are completely inconsistent, as previously reported for the t-Bu+ cation [Stoyanov E. S., et al. J. Phys. Chem. A, 2015, 119, 8619]. This means that the generally accepted explanation of hyperconjugative stabilization of the carbocations should be revised. According to the theory, one CH bond (denoted as CHClubsuit sign) from each CH3/CH2 group transfers its σ-electron density to the empty 2pz orbital of the sp2 C atom, whereas the σ-electron density on the other CH bonds of the CH3/CH2 group slightly increases. From experimental IR spectra it follows that donation of the σ-electrons from the CHClubsuit sign bond to the 2pz C-orbital is accompanied by equal withdrawal of the electron density from other CH bonds, that is, the electrons are supplied from each CH bond of the CH3/CH2 group. As a result, all CH stretches of the group are red shifted, and IR spectra show typical CH3/CH2 group vibrations. Experimental findings provided another clue to the electron distribution in the hydrocarbon cations and showed that the standard computational techniques do not allow researchers to explain a number of recently established features of the molecular state of hydrocarbon cations.

KW - STABLE CARBONIUM-IONS

KW - BUTYL CATION

KW - CONDENSED PHASES

KW - HYPERCONJUGATION

KW - PROTONATION

KW - ENERGETICS

KW - CHEMISTRY

UR - http://www.scopus.com/inward/record.url?scp=85015784916&partnerID=8YFLogxK

U2 - 10.1039/c6cp06839a

DO - 10.1039/c6cp06839a

M3 - Article

C2 - 28239699

AN - SCOPUS:85015784916

VL - 19

SP - 7270

EP - 7279

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 10

ER -

ID: 9053498