Calculated polar substituent effects on the stability of 4-substituted(X) - cub-1-yl and -bicyclo[2.2.2]oct-1-yl cations: a DFT study

William Adcock

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    2 Citations (Scopus)

    Abstract

    The effects of substituents on the stability of 4-substituted(X) cub-1-yl cations (2), as well as the benchmark 4-substituted(X) bicyclo[2.2.2]oct-1-yl cation systems (7), for a set of substituents (X = H, NO2, CN, NC, CF3, COOH, F, Cl, HO, NH2, CH3, SiH 3, Si(CH3)3, Li, O-, and NH 3+) covering a wide range of electronic substituent effects were calculated using the DFT theoretical model at the B3LYP/6-311 + G(2d,p) level of theory. Linear regression analysis was employed to explore the relationship between the calculated relative hydride affinities (ΔE, kcal/mol) of the appropriate isodesmic reactions for 2/7 and polar field/group electronegativity substituent constants (σF and σχ, respectively). The analysis reveals that the ΔE values of both systems are best described by a combination of both substituent constants. This highlights the distinction between through-space and through-bond electronic influences characterized by σF and σχ, respectively.

    Original languageEnglish
    Pages (from-to)513-516
    Number of pages4
    JournalJournal of Physical Organic Chemistry
    Volume24
    Issue number6
    DOIs
    Publication statusPublished - Jun 2011

    Keywords

    • B3LYP/6-311 + G(2d,p)
    • bicycle[2.2.2]octane
    • cubane
    • DFT
    • electronic effects
    • regression analysis
    • substituent effects

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