Mechanistic study of the complex formation of boric acid

Koji Ishihara, Yasuko Mouri, Shigenobu Funahashi, Motoharu Tanaka

    Research output: Contribution to journalArticle

    43 Citations (Scopus)

    Abstract

    Trigonal boric acid, B(OH)3, reacts with bidentate ligands like 4-isopropyltropolone (Hipt) and chromotropic acid (1,8-dihydroxynaphthalene-3,6-disulfonate, H2cht2-) and a tridentate H-resorcinol (1-((2,4-dihydroxy-1-phenyl)azo)-8-hydroxynaphthalene-3,6-disulfonate, H2res2-) to form the 1:1 complex. The reactions are represented as follows: B(OH)3 + Hipt ⇌kd kf B(OH)2(ipt) + H2O B(OH)3 + H2cht2-kd kf B(OH)2(cht)3- + H3O+ B(OH)3 + H2res2-kf B(OH)(res)2- + 2H2O Kinetic measurements were carried out at various temperatures and pressures by using a high-pressure stopped-flow apparatus with spectrophotometric detection. Rate constants (25°C) and activation parameters obtained at I = 0.10 M (NaClO4) are as follows: kf = 144 M-1 s-1, kd = 0.561 s-1, ΔHf* = 26.2 ± 0.7 kJ mol-1, ΔHd = 68.1 ± 1.2 kJ mol-1, ΔSf , = -116 ± 4 J mol-1 K-1, ΔSd = -21 ± 4 J mol-1 K-1, ΔVf = -9.9 ± 0.3 cm3 mol-1 (25°C), and ΔVd = -7.1 ± 0.4 cm3 mol-1 (25°C) for the Hipt reaction; kf = 1.38 × 103 M-1 s-1, kd = 1.61 × 104 M-1 s-1, ΔHf = 12.9 ± 1.5 kJ mol-1, ΔHd = 45.5 ± 0.6 kJ mol-1, ΔSf = -141 ± 5 J mol-1 K-1, ΔSd = -12 ± 4 J mol-1 K-1, ΔVf = -15.3 ± 1.9 cm3 mol-1 (20°C), and ΔVd = -6.3 ± 0.7 cm3 mol-1 (20°C) for the H2cht2- reaction; kf = 1.01 M-1 s-1, ΔHf = 45.2 ± 0.8 kJ mol-1, ΔSf = -93 ± 4 J mol-1 K-1, and ΔVf = 3.9 ± 0.4 cm3 mol-1 (25°C) for the H2res2- reaction. For the bidentate Hipt and H2cht2-, the rate-determining step is the change in the coordination environment of boron from trigonal to tetrahedral, while for the tridentate, H2res2-, the subsequent chelate-ring closure is rate limiting.

    Original languageEnglish
    Pages (from-to)2356-2360
    Number of pages5
    JournalInorganic Chemistry
    Volume30
    Issue number10
    Publication statusPublished - 1991

    Fingerprint

    boric acids
    Naphthols
    Boron
    Rate constants
    Chemical activation
    Ligands
    Kinetics
    chelates
    closures
    boron
    activation
    Temperature
    ligands
    acids
    boric acid
    rings
    kinetics
    temperature
    resorcinol
    1,8-dihydroxynaphthalene

    ASJC Scopus subject areas

    • Inorganic Chemistry

    Cite this

    Ishihara, K., Mouri, Y., Funahashi, S., & Tanaka, M. (1991). Mechanistic study of the complex formation of boric acid. Inorganic Chemistry, 30(10), 2356-2360.

    Mechanistic study of the complex formation of boric acid. / Ishihara, Koji; Mouri, Yasuko; Funahashi, Shigenobu; Tanaka, Motoharu.

    In: Inorganic Chemistry, Vol. 30, No. 10, 1991, p. 2356-2360.

    Research output: Contribution to journalArticle

    Ishihara, K, Mouri, Y, Funahashi, S & Tanaka, M 1991, 'Mechanistic study of the complex formation of boric acid', Inorganic Chemistry, vol. 30, no. 10, pp. 2356-2360.
    Ishihara K, Mouri Y, Funahashi S, Tanaka M. Mechanistic study of the complex formation of boric acid. Inorganic Chemistry. 1991;30(10):2356-2360.
    Ishihara, Koji ; Mouri, Yasuko ; Funahashi, Shigenobu ; Tanaka, Motoharu. / Mechanistic study of the complex formation of boric acid. In: Inorganic Chemistry. 1991 ; Vol. 30, No. 10. pp. 2356-2360.
    @article{3e7d13642aa44039aed78163cc59efd5,
    title = "Mechanistic study of the complex formation of boric acid",
    abstract = "Trigonal boric acid, B(OH)3, reacts with bidentate ligands like 4-isopropyltropolone (Hipt) and chromotropic acid (1,8-dihydroxynaphthalene-3,6-disulfonate, H2cht2-) and a tridentate H-resorcinol (1-((2,4-dihydroxy-1-phenyl)azo)-8-hydroxynaphthalene-3,6-disulfonate, H2res2-) to form the 1:1 complex. The reactions are represented as follows: B(OH)3 + Hipt ⇌kd kf B(OH)2(ipt) + H2O B(OH)3 + H2cht2- ⇌kd kf B(OH)2(cht)3- + H3O+ B(OH)3 + H2res2- →kf B(OH)(res)2- + 2H2O Kinetic measurements were carried out at various temperatures and pressures by using a high-pressure stopped-flow apparatus with spectrophotometric detection. Rate constants (25°C) and activation parameters obtained at I = 0.10 M (NaClO4) are as follows: kf = 144 M-1 s-1, kd = 0.561 s-1, ΔHf* = 26.2 ± 0.7 kJ mol-1, ΔHd ‡ = 68.1 ± 1.2 kJ mol-1, ΔSf ‡, = -116 ± 4 J mol-1 K-1, ΔSd ‡ = -21 ± 4 J mol-1 K-1, ΔVf ‡ = -9.9 ± 0.3 cm3 mol-1 (25°C), and ΔVd ‡ = -7.1 ± 0.4 cm3 mol-1 (25°C) for the Hipt reaction; kf = 1.38 × 103 M-1 s-1, kd = 1.61 × 104 M-1 s-1, ΔHf ‡ = 12.9 ± 1.5 kJ mol-1, ΔHd ‡ = 45.5 ± 0.6 kJ mol-1, ΔSf ‡ = -141 ± 5 J mol-1 K-1, ΔSd ‡ = -12 ± 4 J mol-1 K-1, ΔVf ‡ = -15.3 ± 1.9 cm3 mol-1 (20°C), and ΔVd ‡ = -6.3 ± 0.7 cm3 mol-1 (20°C) for the H2cht2- reaction; kf = 1.01 M-1 s-1, ΔHf ‡ = 45.2 ± 0.8 kJ mol-1, ΔSf ‡ = -93 ± 4 J mol-1 K-1, and ΔVf ‡ = 3.9 ± 0.4 cm3 mol-1 (25°C) for the H2res2- reaction. For the bidentate Hipt and H2cht2-, the rate-determining step is the change in the coordination environment of boron from trigonal to tetrahedral, while for the tridentate, H2res2-, the subsequent chelate-ring closure is rate limiting.",
    author = "Koji Ishihara and Yasuko Mouri and Shigenobu Funahashi and Motoharu Tanaka",
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    TY - JOUR

    T1 - Mechanistic study of the complex formation of boric acid

    AU - Ishihara, Koji

    AU - Mouri, Yasuko

    AU - Funahashi, Shigenobu

    AU - Tanaka, Motoharu

    PY - 1991

    Y1 - 1991

    N2 - Trigonal boric acid, B(OH)3, reacts with bidentate ligands like 4-isopropyltropolone (Hipt) and chromotropic acid (1,8-dihydroxynaphthalene-3,6-disulfonate, H2cht2-) and a tridentate H-resorcinol (1-((2,4-dihydroxy-1-phenyl)azo)-8-hydroxynaphthalene-3,6-disulfonate, H2res2-) to form the 1:1 complex. The reactions are represented as follows: B(OH)3 + Hipt ⇌kd kf B(OH)2(ipt) + H2O B(OH)3 + H2cht2- ⇌kd kf B(OH)2(cht)3- + H3O+ B(OH)3 + H2res2- →kf B(OH)(res)2- + 2H2O Kinetic measurements were carried out at various temperatures and pressures by using a high-pressure stopped-flow apparatus with spectrophotometric detection. Rate constants (25°C) and activation parameters obtained at I = 0.10 M (NaClO4) are as follows: kf = 144 M-1 s-1, kd = 0.561 s-1, ΔHf* = 26.2 ± 0.7 kJ mol-1, ΔHd ‡ = 68.1 ± 1.2 kJ mol-1, ΔSf ‡, = -116 ± 4 J mol-1 K-1, ΔSd ‡ = -21 ± 4 J mol-1 K-1, ΔVf ‡ = -9.9 ± 0.3 cm3 mol-1 (25°C), and ΔVd ‡ = -7.1 ± 0.4 cm3 mol-1 (25°C) for the Hipt reaction; kf = 1.38 × 103 M-1 s-1, kd = 1.61 × 104 M-1 s-1, ΔHf ‡ = 12.9 ± 1.5 kJ mol-1, ΔHd ‡ = 45.5 ± 0.6 kJ mol-1, ΔSf ‡ = -141 ± 5 J mol-1 K-1, ΔSd ‡ = -12 ± 4 J mol-1 K-1, ΔVf ‡ = -15.3 ± 1.9 cm3 mol-1 (20°C), and ΔVd ‡ = -6.3 ± 0.7 cm3 mol-1 (20°C) for the H2cht2- reaction; kf = 1.01 M-1 s-1, ΔHf ‡ = 45.2 ± 0.8 kJ mol-1, ΔSf ‡ = -93 ± 4 J mol-1 K-1, and ΔVf ‡ = 3.9 ± 0.4 cm3 mol-1 (25°C) for the H2res2- reaction. For the bidentate Hipt and H2cht2-, the rate-determining step is the change in the coordination environment of boron from trigonal to tetrahedral, while for the tridentate, H2res2-, the subsequent chelate-ring closure is rate limiting.

    AB - Trigonal boric acid, B(OH)3, reacts with bidentate ligands like 4-isopropyltropolone (Hipt) and chromotropic acid (1,8-dihydroxynaphthalene-3,6-disulfonate, H2cht2-) and a tridentate H-resorcinol (1-((2,4-dihydroxy-1-phenyl)azo)-8-hydroxynaphthalene-3,6-disulfonate, H2res2-) to form the 1:1 complex. The reactions are represented as follows: B(OH)3 + Hipt ⇌kd kf B(OH)2(ipt) + H2O B(OH)3 + H2cht2- ⇌kd kf B(OH)2(cht)3- + H3O+ B(OH)3 + H2res2- →kf B(OH)(res)2- + 2H2O Kinetic measurements were carried out at various temperatures and pressures by using a high-pressure stopped-flow apparatus with spectrophotometric detection. Rate constants (25°C) and activation parameters obtained at I = 0.10 M (NaClO4) are as follows: kf = 144 M-1 s-1, kd = 0.561 s-1, ΔHf* = 26.2 ± 0.7 kJ mol-1, ΔHd ‡ = 68.1 ± 1.2 kJ mol-1, ΔSf ‡, = -116 ± 4 J mol-1 K-1, ΔSd ‡ = -21 ± 4 J mol-1 K-1, ΔVf ‡ = -9.9 ± 0.3 cm3 mol-1 (25°C), and ΔVd ‡ = -7.1 ± 0.4 cm3 mol-1 (25°C) for the Hipt reaction; kf = 1.38 × 103 M-1 s-1, kd = 1.61 × 104 M-1 s-1, ΔHf ‡ = 12.9 ± 1.5 kJ mol-1, ΔHd ‡ = 45.5 ± 0.6 kJ mol-1, ΔSf ‡ = -141 ± 5 J mol-1 K-1, ΔSd ‡ = -12 ± 4 J mol-1 K-1, ΔVf ‡ = -15.3 ± 1.9 cm3 mol-1 (20°C), and ΔVd ‡ = -6.3 ± 0.7 cm3 mol-1 (20°C) for the H2cht2- reaction; kf = 1.01 M-1 s-1, ΔHf ‡ = 45.2 ± 0.8 kJ mol-1, ΔSf ‡ = -93 ± 4 J mol-1 K-1, and ΔVf ‡ = 3.9 ± 0.4 cm3 mol-1 (25°C) for the H2res2- reaction. For the bidentate Hipt and H2cht2-, the rate-determining step is the change in the coordination environment of boron from trigonal to tetrahedral, while for the tridentate, H2res2-, the subsequent chelate-ring closure is rate limiting.

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