Bulletin of the Korean Chemical Society

  • 제16권11호
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  • Pages.1104-1108
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  • 1995
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  • 0253-2964(pISSN)
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  • 1229-5949(eISSN)
대한화학회 (Korean Chemical Society)
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Solvent Effects on Localized and Delocalized Cationic Charges in Solvolysis$^1$

  • 발행 : 1995.11.20
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초록

A measure of stabilities (-ΔHo) and resonance delocalization (-Δq(Cα+)) for some carbocations has been estimated using the semiempirical AM1 method. The stability (-ΔHo) of carbocations can be correlated with the sensitivity (m) of localized cations to the solvent ionizing power scale Y, whereas the extent of resonance delocalization (-Δq(Cα+)) can be correlated with the sensitivity (h) of delocalized cations to the solvent ionizing power scale Ⅰ. It has been shown that two solvent ionizing power scales Y and I have in general opposite signs so that effects of electrostatic solvation are opposite for the localized and delocalized cationic charges. The use of two different solvent scales for a substrate with delocalizable cationic charge is not only prerequisite to the proper correlation of solvolysis rates but also is justified.

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참고문헌

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