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Chemistry (HMC)

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In this study, we calculate the stabilization of β-substituted ethyl cations (R = H, Li, BeH, BH_2, CH_3, NH_2, OH, F, Na, MgH, AlH_2, SiH_3, PH_2, SH, Cl) and α-substituted methyl cations (R = H, Li, CH_3, NH_2, OH, F, Na, SiH_3, PH_2, SH, Cl) in order to obtain a relationship between the nature of the substituent and the degree of stabilization of the cation. Results show that the stabilization energy is related to the electronegativity of the β substituents, but not the α substituents. The rotational barrier of the β-substituted ethyl cation is linearly related to the Mulliken population of the 2p(C+) orbital. We found that the stabilization energy is linearly related to the ionization potential of the α- and PLA β-substituted radicals, and the HOMO energies of the PLA β-substituted radical are linearly related to the corresponding ionization potentials. Trends in the stabilization by second- and third-row substituents are discussed.

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© 1988 American Chemical Society

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