A dataset of highly accurate homolytic NBr bond dissociation energies obtained by Means of W2 theory

Robert J. O'Reilly, Amir Karton

    Research output: Contribution to journalArticle

    18 Citations (Scopus)

    Abstract

    Homolytic NBr bond dissociation constitutes the initial step of numerous reactions involving N-brominated species. However, little is known about the strength of NBr bonds toward homolytic cleavage. We herein report accurate bond dissociation energies (BDEs) for a set of 18 molecules using the high-level W2 thermochemical protocol. The BDEs (at 298 K) of the species in this set range from 162.2 kJ mol-1 (N-bromopyrrole) to 260.6 kJ mol-1 ((CHO)2NBr). In order to compute BDEs of larger systems, for which W2 theory is not applicable, we have benchmarked a wide range of more economical theoretical procedures. Of these, G3-B3 offers the best performance (root-mean-square deviations = 2.9 kJ mol-1), and using this method, we have computed NBr BDEs for four widely used N-brominated compounds. These include (BDEs are given in parentheses): N-bromosuccinimide (281.6), N-bromoglutarimide (263.2), N-bromophthalimide (274.7), and 1,3-dibromo-5,5-dimethylhydantoin (218.2 and 264.8 kJ mol-1).

    Original languageEnglish
    Pages (from-to)52-60
    Number of pages9
    JournalInternational Journal of Quantum Chemistry
    Volume116
    Issue number1
    DOIs
    Publication statusPublished - Jan 5 2016

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    dissociation
    energy
    Bromosuccinimide
    cleavage
    deviation
    Molecules
    molecules

    Keywords

    • CCSD(T)
    • density functional theory
    • Gaussian-n
    • N-bromamine
    • N-bromoamide
    • N-bromoimide
    • W2 theory

    ASJC Scopus subject areas

    • Condensed Matter Physics
    • Atomic and Molecular Physics, and Optics
    • Physical and Theoretical Chemistry

    Cite this

    A dataset of highly accurate homolytic NBr bond dissociation energies obtained by Means of W2 theory. / O'Reilly, Robert J.; Karton, Amir.

    In: International Journal of Quantum Chemistry, Vol. 116, No. 1, 05.01.2016, p. 52-60.

    Research output: Contribution to journalArticle

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