Relative kinetic reactivities of boronic acids and boronate ions toward 1,2-diols

Takuya Okamoto, Asumi Tanaka, Eisuke Watanabe, Takehiro Miyazaki, Tomoaki Sugaya, Satoshi Iwatsuki, Masahiko Inamo, Hideo D. Takagi, Akira Odani, Koji Ishihara

    Research output: Contribution to journalArticle

    14 Citations (Scopus)

    Abstract

    The following reaction systems, with and without proton ambiguity, were set up for direct measurements of the rate constants of borate and boronate ions: boric acid [B(OH)3] and 4,5-dihydroxy-1,3-benzenedisulfonic acid disodium salt (Tiron); 3-nitrophenylboronic acid [3-NO2PhB(OH) 2] and Tiron; phenylboronic acid [PhB(OH)2] and 4-nitrocatechol; boric acid and 4-nitrocatechol. Each rate constant for boric or boronic acid is larger than that for the conjugate borate or boronate ion for the reaction systems without proton ambiguity. These results explicitly indicate that the widespread belief that the rate constants of boronate ions are several orders of magnitude larger than those of the conjugate boronic acids is erroneous. The relative kinetic reactivities of RB(OH)2 and RB(OH)3 - were investigated in relation to the linear free energy relationships between the rate constants and acidities of the boronic acids and diols. Kinetic results clearly show that boronic acids are more reactive than their respective conjugate boronate ions. This corrects the erroneous conclusion that the boronate ion reacts faster than its conjugate boronic acid by at least several orders of magnitude. The relative kinetic reactivities of boric acid and boronate ions are discussed in terms of mechanistic differences.

    Original languageEnglish
    Pages (from-to)2389-2395
    Number of pages7
    JournalEuropean Journal of Inorganic Chemistry
    Issue number14
    DOIs
    Publication statusPublished - 2014

    Fingerprint

    Boronic Acids
    1,2-Dihydroxybenzene-3,5-Disulfonic Acid Disodium Salt
    Ions
    Kinetics
    Rate constants
    Borates
    Protons
    Acidity
    Free energy
    boric acid

    Keywords

    • Boron
    • Boronates
    • Boronic acids
    • Kinetics
    • Reaction mechanisms

    ASJC Scopus subject areas

    • Inorganic Chemistry

    Cite this

    Relative kinetic reactivities of boronic acids and boronate ions toward 1,2-diols. / Okamoto, Takuya; Tanaka, Asumi; Watanabe, Eisuke; Miyazaki, Takehiro; Sugaya, Tomoaki; Iwatsuki, Satoshi; Inamo, Masahiko; Takagi, Hideo D.; Odani, Akira; Ishihara, Koji.

    In: European Journal of Inorganic Chemistry, No. 14, 2014, p. 2389-2395.

    Research output: Contribution to journalArticle

    Okamoto, T, Tanaka, A, Watanabe, E, Miyazaki, T, Sugaya, T, Iwatsuki, S, Inamo, M, Takagi, HD, Odani, A & Ishihara, K 2014, 'Relative kinetic reactivities of boronic acids and boronate ions toward 1,2-diols', European Journal of Inorganic Chemistry, no. 14, pp. 2389-2395. https://doi.org/10.1002/ejic.201400040
    Okamoto, Takuya ; Tanaka, Asumi ; Watanabe, Eisuke ; Miyazaki, Takehiro ; Sugaya, Tomoaki ; Iwatsuki, Satoshi ; Inamo, Masahiko ; Takagi, Hideo D. ; Odani, Akira ; Ishihara, Koji. / Relative kinetic reactivities of boronic acids and boronate ions toward 1,2-diols. In: European Journal of Inorganic Chemistry. 2014 ; No. 14. pp. 2389-2395.
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    AU - Sugaya, Tomoaki

    AU - Iwatsuki, Satoshi

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    AB - The following reaction systems, with and without proton ambiguity, were set up for direct measurements of the rate constants of borate and boronate ions: boric acid [B(OH)3] and 4,5-dihydroxy-1,3-benzenedisulfonic acid disodium salt (Tiron); 3-nitrophenylboronic acid [3-NO2PhB(OH) 2] and Tiron; phenylboronic acid [PhB(OH)2] and 4-nitrocatechol; boric acid and 4-nitrocatechol. Each rate constant for boric or boronic acid is larger than that for the conjugate borate or boronate ion for the reaction systems without proton ambiguity. These results explicitly indicate that the widespread belief that the rate constants of boronate ions are several orders of magnitude larger than those of the conjugate boronic acids is erroneous. The relative kinetic reactivities of RB(OH)2 and RB(OH)3 - were investigated in relation to the linear free energy relationships between the rate constants and acidities of the boronic acids and diols. Kinetic results clearly show that boronic acids are more reactive than their respective conjugate boronate ions. This corrects the erroneous conclusion that the boronate ion reacts faster than its conjugate boronic acid by at least several orders of magnitude. The relative kinetic reactivities of boric acid and boronate ions are discussed in terms of mechanistic differences.

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