Calculated polar substituent effects on the stability of 3-substituted(X) bicyclo[1.1.1]pent-1-yl cations and 4-substituted(X) bicyclo[2.2.1]hept-1-yl cations: a DFT study

William Adcock

    Research output: Contribution to journalArticle

    2 Citations (Scopus)

    Abstract

    The effects of substituents on the stability of 3-substituted(X) bicyclo[1.1.1]pent-1-yl cations (3) and 4-substituted(X) bicyclo[2.2.1]hept-1-yl cations (4), for a set of substituents (X = H, NO2, CN, NC, CF 3, CHO, 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) and B3LYP/6-31 + G (d) levels of theory, respectively. Linear regression analysis was employed to explore the relationship between the calculated relative hydride affinities (ΔE, kcal/mol) of the appropriate isodesmic reactions for 3/4 and polar field/group electronegativity substituent constants (σF and σχ, respectively). The analysis reveals that the ΔE values for both systems are best described by a combination of both substituent constants. The result highlights the importance of the σχ dependency of charge delocalization in these systems.

    Original languageEnglish
    Pages (from-to)1404-1408
    Number of pages5
    JournalJournal of Physical Organic Chemistry
    Volume25
    Issue number12
    DOIs
    Publication statusPublished - Dec 2012

    Keywords

    • B3LYP/6-311 + G(2d,p)
    • bicyclo[1.1.1]pentane
    • bicyclo[2.2.1]heptane
    • density functional theory (DFT)
    • electronic effects
    • regression analysis
    • substituent effects

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