Cation-pi interactions in the gas phase methylation of alpha,omega-diphenylalkanes

Chiavarino B, Crestoni ME, Fornarini S, Kuck D (2003)
JOURNAL OF PHYSICAL CHEMISTRY A 107(23): 4619-4624.

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Abstract
The methylation of alpha,omega-diphenylalkanes (C6H5(CH2)(n)C6H5, n = 1-6) has been performed in the gas phase using Me2Cl+ ions as alkylating species and toluene as reference substrate. Both in radiolytic experiments at atmospheric pressure and in FT-ICR measurements at 10(-8) Torr, the selected diphenylalkanes reacted faster than toluene, the highest reactivity displayed by 1,3-diphenylpropane. The kinetic pattern of the reaction, conforming to the established scheme of an electrophilic alkylation reaction, is consistent with a rate-determining formation of the sigma-complex intermediate, at variance with the tert-butylation of the same series of compounds by Me3C+ ions, occurring at the collisional encounter rate. The kinetic features are explained by a marked effect due to the presence of the second aryl ring, providing additional stabilization of both the ion-neutral collision complex and the sigma complex with respect to toluene. Both factors contribute to the deltaE(a) of ca. 8 kcal mol(-1) for the competition of 1,3-diphenylpropane and toluene found in the temperature dependence study of the Me2Cl+ reaction.
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Chiavarino B, Crestoni ME, Fornarini S, Kuck D. Cation-pi interactions in the gas phase methylation of alpha,omega-diphenylalkanes. JOURNAL OF PHYSICAL CHEMISTRY A. 2003;107(23):4619-4624.
Chiavarino, B., Crestoni, M. E., Fornarini, S., & Kuck, D. (2003). Cation-pi interactions in the gas phase methylation of alpha,omega-diphenylalkanes. JOURNAL OF PHYSICAL CHEMISTRY A, 107(23), 4619-4624.
Chiavarino, B., Crestoni, M. E., Fornarini, S., and Kuck, D. (2003). Cation-pi interactions in the gas phase methylation of alpha,omega-diphenylalkanes. JOURNAL OF PHYSICAL CHEMISTRY A 107, 4619-4624.
Chiavarino, B., et al., 2003. Cation-pi interactions in the gas phase methylation of alpha,omega-diphenylalkanes. JOURNAL OF PHYSICAL CHEMISTRY A, 107(23), p 4619-4624.
B. Chiavarino, et al., “Cation-pi interactions in the gas phase methylation of alpha,omega-diphenylalkanes”, JOURNAL OF PHYSICAL CHEMISTRY A, vol. 107, 2003, pp. 4619-4624.
Chiavarino, B., Crestoni, M.E., Fornarini, S., Kuck, D.: Cation-pi interactions in the gas phase methylation of alpha,omega-diphenylalkanes. JOURNAL OF PHYSICAL CHEMISTRY A. 107, 4619-4624 (2003).
Chiavarino, B., Crestoni, M. E., Fornarini, S., and Kuck, Dietmar. “Cation-pi interactions in the gas phase methylation of alpha,omega-diphenylalkanes”. JOURNAL OF PHYSICAL CHEMISTRY A 107.23 (2003): 4619-4624.
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