Stabilization of carbocations CH3+, C2H5+, i-C3H7+, tert-Bu+, and cyclo-pentyl+ in solid phases: experimental data versus calculations

Evgenii S Stoyanov; Anton S Nizovtsev

doi:10.1039/c6cp06839a

Stabilization of carbocations CH₃⁺, C₂H₅⁺, i-C₃H₇⁺, tert-Bu⁺, and cyclo-pentyl⁺ in solid phases: experimental data versus calculations

Phys Chem Chem Phys. 2017 Mar 8;19(10):7270-7279. doi: 10.1039/c6cp06839a.

Authors

Evgenii S Stoyanov¹, Anton S Nizovtsev²

Affiliations

¹ Vorozhtsov Institute of Organic Chemistry, Siberian Branch of Russian Academy of Sciences, Novosibirsk 630090, Russia. evgenii@nioch.nsc.ru and Department of Natural Sciences, National Research University, Novosibirsk State University, Novosibirsk 630090, Russia.
² Department of Natural Sciences, National Research University, Novosibirsk State University, Novosibirsk 630090, Russia and Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, Novosibirsk 630090, Russia.

PMID: 28239699
DOI: 10.1039/c6cp06839a

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 ) from each CH₃/CH₂ group transfers its σ-electron density to the empty 2p_z 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 bond to the 2p_z 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.