Universal Reaction Mechanism of Boronic Acids with Diols in Aqueous Solution: Kinetics and the Basic Concept of a Conditional Formation Constant

Yuki Furikado, Tomomi Nagahata, Takuya Okamoto, Tomoaki Sugaya, Satoshi Iwatsuki, Masahiko Inamo, Hideo D. Takagi, Akira Odani, Koji Ishihara

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    35 Citations (Scopus)

    Abstract

    To establish a detailed reaction mechanism for the condensation between a boronic acid, RB(OH)2, and a diol, H2L, in aqueous solution, the acid dissociation constants ({K{{{\rm BL}\hfill \atop {\rm a}\hfill}}}) of boronic acid diol esters (HBLs) were determined based on the well-established concept of conditional formation constants of metal complexes. The pKa values of HBLs were 2.30, 2.77, and 2.00 for the reaction systems, 2,4-difluorophenylboronic acid and chromotropic acid, 3-nitrophenylboronic acid and alizarin red S, and phenylboronic acid and alizarin red S, respectively. A general and precise reaction mechanism of RB(OH)2 with H2L in aqueous solution, which can serve as a universal reaction mechanism for RB(OH)2 and H2L, was proposed on the basis of (a) the relative kinetic reactivities of the RB(OH)2 and its conjugate base, that is, the boronate ion, toward H2L, and (b) the determined pKa values of HBLs. The use of the conditional formation constant, K′, based on the main reaction: [eq found] instead of the binding constant has been proposed for the general reaction of uncomplexed boronic acid species (B′) with uncomplexed diol species (L′) to form boronic acid diol complex species (esters, BL′) in aqueous solution at pH 5-11: [eq found]. The proposed reaction mechanism explains perfectly the formation of boronic acid diol ester in aqueous solution. Using the conditional formation constant (K′) instead of the binding constant allows one to determine a detailed reaction mechanism for the reaction between boronic acids (RB(OH)2) and diols (H2L) in aqueous solution. The proposed mechanism based on thermodynamic and kinetic data explains perfectly the formation of boronic acid diol esters, RB(L)(OH)-.

    Original languageEnglish
    Pages (from-to)13194-13202
    Number of pages9
    JournalChemistry - A European Journal
    Volume20
    Issue number41
    DOIs
    Publication statusPublished - 2014 Oct 1

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    Keywords

    • boronate ion
    • boronic acid
    • conditional formation constant
    • kinetics
    • mechanism

    ASJC Scopus subject areas

    • Chemistry(all)

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