Kinetic study of the ligand substitution on the trimethylplatinum(IV) complexes with unidentate ligands

Yuichi Kondo, Yumi Oda, Koji Ishihara

    Research output: Contribution to journalArticle

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    Abstract

    Ligand substitution kinetics for the reaction [PtIVMe3(X)(NN)] + NaY = [PtIVMe3(Y)(NN)] + NaX, where NN = bipy or phen, X = MeO-, CH3COO-, or HCOO-, and Y = SCN- or N3 -, has been studied in methanol at various temperatures. The kinetic parameters for the reaction are as follows. The reaction of [PtMe3(OMe)(phen)] with NaSCN: k1 = 36.1 ± 10.0 s-1; ΔH1 = 65.9 ± 14.2 kj mol-1; ΔS1 = 6 ± 47 J mol-1 K-1; k2 = 0.0355 ± 0.0034 s-1; ΔH-2 = 63.8 ± 1.1 kJ mol-1; ΔS-2 = -58.8 ± 3.6 J mol-1 K-1; and k-1/k2 = 148 ± 19. The reaction of [PtMe3(OAc)(bipy)] with NaN3: k1 = 26.2 ± 0.1 s-1; ΔH1 = 60.5 ± 6.6 kJ mol-1; ΔS1 = -14 ± 22 J mol-1K-1; k-2 = 0.134 ± 0.081 s-1; ΔH-2 = 74.1 ± 24.3 kJ mol-1; ΔS-2 = -10 ± 82 J mol-1K-1; and k-1/k2 = 0.479 ± 0.012. The reaction of [PtMe3(OAc)(bipy)] with NaSCN; k1 = 26.4 ± 0.3 s-1; ΔH1 = 59.6 ± 6.7 kJ mol-1; ΔS1 = -17 ± 23 J mol-1K-1; k-2 = 0.174 ± 0.200 s-1; ΔH-2 = 62.7 ± 10.3 kJ mol-1; ΔS-2 = -48 ± 35 J mol-1K-1 and k-1/k2 = 1.01 ± 0.08. The reaction of [PtMe3(OOCH)(bipy)] with NaN3: k1 = 36.8 ± 0.3 s-1; ΔH1 = 66.4 ± 4.7 kJ mol-1; ΔS1 = 7 ± 16 J mol-1K-1; k-2 = 0.164 ± 0.076 s-1; ΔH-2 = 47.0 ± 18.1 kJ mol-1; ΔS-2 = -101 ± 61 J mol-1 K-1; and k-1/k2 = 5.90 ± 0.18. The reaction of [PtMe3(OOCH)(bipy)] with NaSCN: k1 = 33.5 ± 0.2 s-1; ΔH1 = 58.0 ± 0.4 kJ mol-1; ΔS1 = -20.5 ± 1.6 J mol-1 K-1; k-2 = 0.222 ± 0.083 s-1; ΔH-2 = 54.9 ± 6.3 kJ mol-1; ΔS-2 = -73.0 ± 21.3 J mol-1 K-1; and k-1/k2 = 12.0 ± 0.3. Conditional pseudo-first-order rate constant k0 increased linearly with the concentration of NaY, while it decreased drastically with the concentration of NaX. Some plausible mechanisms were examined, and the following mechanism was proposed.>

    Original languageEnglish
    Pages (from-to)523-532
    Number of pages10
    JournalInternational Journal of Chemical Kinetics
    Volume30
    Issue number8
    Publication statusPublished - 1998

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    Kinetic parameters
    Rate constants
    Sodium Azide
    Methanol
    Substitution reactions
    Ligands
    substitutes
    ligands
    Kinetics
    kinetics
    Temperature
    sodium thiocyanate
    methyl alcohol

    ASJC Scopus subject areas

    • Catalysis
    • Physical and Theoretical Chemistry

    Cite this

    Kinetic study of the ligand substitution on the trimethylplatinum(IV) complexes with unidentate ligands. / Kondo, Yuichi; Oda, Yumi; Ishihara, Koji.

    In: International Journal of Chemical Kinetics, Vol. 30, No. 8, 1998, p. 523-532.

    Research output: Contribution to journalArticle

    @article{75132587b3ac47d8bf9a66131f051256,
    title = "Kinetic study of the ligand substitution on the trimethylplatinum(IV) complexes with unidentate ligands",
    abstract = "Ligand substitution kinetics for the reaction [PtIVMe3(X)(NN)] + NaY = [PtIVMe3(Y)(NN)] + NaX, where NN = bipy or phen, X = MeO-, CH3COO-, or HCOO-, and Y = SCN- or N3 -, has been studied in methanol at various temperatures. The kinetic parameters for the reaction are as follows. The reaction of [PtMe3(OMe)(phen)] with NaSCN: k1 = 36.1 ± 10.0 s-1; ΔH1 ≠ = 65.9 ± 14.2 kj mol-1; ΔS1 ≠ = 6 ± 47 J mol-1 K-1; k2 = 0.0355 ± 0.0034 s-1; ΔH-2 ≠ = 63.8 ± 1.1 kJ mol-1; ΔS-2 ≠ = -58.8 ± 3.6 J mol-1 K-1; and k-1/k2 = 148 ± 19. The reaction of [PtMe3(OAc)(bipy)] with NaN3: k1 = 26.2 ± 0.1 s-1; ΔH1 ≠ = 60.5 ± 6.6 kJ mol-1; ΔS1 ≠ = -14 ± 22 J mol-1K-1; k-2 = 0.134 ± 0.081 s-1; ΔH-2 ≠ = 74.1 ± 24.3 kJ mol-1; ΔS-2 ≠ = -10 ± 82 J mol-1K-1; and k-1/k2 = 0.479 ± 0.012. The reaction of [PtMe3(OAc)(bipy)] with NaSCN; k1 = 26.4 ± 0.3 s-1; ΔH1 ≠ = 59.6 ± 6.7 kJ mol-1; ΔS1 ≠ = -17 ± 23 J mol-1K-1; k-2 = 0.174 ± 0.200 s-1; ΔH-2 ≠ = 62.7 ± 10.3 kJ mol-1; ΔS-2 ≠ = -48 ± 35 J mol-1K-1 and k-1/k2 = 1.01 ± 0.08. The reaction of [PtMe3(OOCH)(bipy)] with NaN3: k1 = 36.8 ± 0.3 s-1; ΔH1 ≠ = 66.4 ± 4.7 kJ mol-1; ΔS1 ≠ = 7 ± 16 J mol-1K-1; k-2 = 0.164 ± 0.076 s-1; ΔH-2 ≠ = 47.0 ± 18.1 kJ mol-1; ΔS-2 ≠ = -101 ± 61 J mol-1 K-1; and k-1/k2 = 5.90 ± 0.18. The reaction of [PtMe3(OOCH)(bipy)] with NaSCN: k1 = 33.5 ± 0.2 s-1; ΔH1 ≠ = 58.0 ± 0.4 kJ mol-1; ΔS1 ≠ = -20.5 ± 1.6 J mol-1 K-1; k-2 = 0.222 ± 0.083 s-1; ΔH-2 ≠ = 54.9 ± 6.3 kJ mol-1; ΔS-2 ≠ = -73.0 ± 21.3 J mol-1 K-1; and k-1/k2 = 12.0 ± 0.3. Conditional pseudo-first-order rate constant k0 increased linearly with the concentration of NaY, while it decreased drastically with the concentration of NaX. Some plausible mechanisms were examined, and the following mechanism was proposed.>",
    author = "Yuichi Kondo and Yumi Oda and Koji Ishihara",
    year = "1998",
    language = "English",
    volume = "30",
    pages = "523--532",
    journal = "International Journal of Chemical Kinetics",
    issn = "0538-8066",
    publisher = "John Wiley and Sons Inc.",
    number = "8",

    }

    TY - JOUR

    T1 - Kinetic study of the ligand substitution on the trimethylplatinum(IV) complexes with unidentate ligands

    AU - Kondo, Yuichi

    AU - Oda, Yumi

    AU - Ishihara, Koji

    PY - 1998

    Y1 - 1998

    N2 - Ligand substitution kinetics for the reaction [PtIVMe3(X)(NN)] + NaY = [PtIVMe3(Y)(NN)] + NaX, where NN = bipy or phen, X = MeO-, CH3COO-, or HCOO-, and Y = SCN- or N3 -, has been studied in methanol at various temperatures. The kinetic parameters for the reaction are as follows. The reaction of [PtMe3(OMe)(phen)] with NaSCN: k1 = 36.1 ± 10.0 s-1; ΔH1 ≠ = 65.9 ± 14.2 kj mol-1; ΔS1 ≠ = 6 ± 47 J mol-1 K-1; k2 = 0.0355 ± 0.0034 s-1; ΔH-2 ≠ = 63.8 ± 1.1 kJ mol-1; ΔS-2 ≠ = -58.8 ± 3.6 J mol-1 K-1; and k-1/k2 = 148 ± 19. The reaction of [PtMe3(OAc)(bipy)] with NaN3: k1 = 26.2 ± 0.1 s-1; ΔH1 ≠ = 60.5 ± 6.6 kJ mol-1; ΔS1 ≠ = -14 ± 22 J mol-1K-1; k-2 = 0.134 ± 0.081 s-1; ΔH-2 ≠ = 74.1 ± 24.3 kJ mol-1; ΔS-2 ≠ = -10 ± 82 J mol-1K-1; and k-1/k2 = 0.479 ± 0.012. The reaction of [PtMe3(OAc)(bipy)] with NaSCN; k1 = 26.4 ± 0.3 s-1; ΔH1 ≠ = 59.6 ± 6.7 kJ mol-1; ΔS1 ≠ = -17 ± 23 J mol-1K-1; k-2 = 0.174 ± 0.200 s-1; ΔH-2 ≠ = 62.7 ± 10.3 kJ mol-1; ΔS-2 ≠ = -48 ± 35 J mol-1K-1 and k-1/k2 = 1.01 ± 0.08. The reaction of [PtMe3(OOCH)(bipy)] with NaN3: k1 = 36.8 ± 0.3 s-1; ΔH1 ≠ = 66.4 ± 4.7 kJ mol-1; ΔS1 ≠ = 7 ± 16 J mol-1K-1; k-2 = 0.164 ± 0.076 s-1; ΔH-2 ≠ = 47.0 ± 18.1 kJ mol-1; ΔS-2 ≠ = -101 ± 61 J mol-1 K-1; and k-1/k2 = 5.90 ± 0.18. The reaction of [PtMe3(OOCH)(bipy)] with NaSCN: k1 = 33.5 ± 0.2 s-1; ΔH1 ≠ = 58.0 ± 0.4 kJ mol-1; ΔS1 ≠ = -20.5 ± 1.6 J mol-1 K-1; k-2 = 0.222 ± 0.083 s-1; ΔH-2 ≠ = 54.9 ± 6.3 kJ mol-1; ΔS-2 ≠ = -73.0 ± 21.3 J mol-1 K-1; and k-1/k2 = 12.0 ± 0.3. Conditional pseudo-first-order rate constant k0 increased linearly with the concentration of NaY, while it decreased drastically with the concentration of NaX. Some plausible mechanisms were examined, and the following mechanism was proposed.>

    AB - Ligand substitution kinetics for the reaction [PtIVMe3(X)(NN)] + NaY = [PtIVMe3(Y)(NN)] + NaX, where NN = bipy or phen, X = MeO-, CH3COO-, or HCOO-, and Y = SCN- or N3 -, has been studied in methanol at various temperatures. The kinetic parameters for the reaction are as follows. The reaction of [PtMe3(OMe)(phen)] with NaSCN: k1 = 36.1 ± 10.0 s-1; ΔH1 ≠ = 65.9 ± 14.2 kj mol-1; ΔS1 ≠ = 6 ± 47 J mol-1 K-1; k2 = 0.0355 ± 0.0034 s-1; ΔH-2 ≠ = 63.8 ± 1.1 kJ mol-1; ΔS-2 ≠ = -58.8 ± 3.6 J mol-1 K-1; and k-1/k2 = 148 ± 19. The reaction of [PtMe3(OAc)(bipy)] with NaN3: k1 = 26.2 ± 0.1 s-1; ΔH1 ≠ = 60.5 ± 6.6 kJ mol-1; ΔS1 ≠ = -14 ± 22 J mol-1K-1; k-2 = 0.134 ± 0.081 s-1; ΔH-2 ≠ = 74.1 ± 24.3 kJ mol-1; ΔS-2 ≠ = -10 ± 82 J mol-1K-1; and k-1/k2 = 0.479 ± 0.012. The reaction of [PtMe3(OAc)(bipy)] with NaSCN; k1 = 26.4 ± 0.3 s-1; ΔH1 ≠ = 59.6 ± 6.7 kJ mol-1; ΔS1 ≠ = -17 ± 23 J mol-1K-1; k-2 = 0.174 ± 0.200 s-1; ΔH-2 ≠ = 62.7 ± 10.3 kJ mol-1; ΔS-2 ≠ = -48 ± 35 J mol-1K-1 and k-1/k2 = 1.01 ± 0.08. The reaction of [PtMe3(OOCH)(bipy)] with NaN3: k1 = 36.8 ± 0.3 s-1; ΔH1 ≠ = 66.4 ± 4.7 kJ mol-1; ΔS1 ≠ = 7 ± 16 J mol-1K-1; k-2 = 0.164 ± 0.076 s-1; ΔH-2 ≠ = 47.0 ± 18.1 kJ mol-1; ΔS-2 ≠ = -101 ± 61 J mol-1 K-1; and k-1/k2 = 5.90 ± 0.18. The reaction of [PtMe3(OOCH)(bipy)] with NaSCN: k1 = 33.5 ± 0.2 s-1; ΔH1 ≠ = 58.0 ± 0.4 kJ mol-1; ΔS1 ≠ = -20.5 ± 1.6 J mol-1 K-1; k-2 = 0.222 ± 0.083 s-1; ΔH-2 ≠ = 54.9 ± 6.3 kJ mol-1; ΔS-2 ≠ = -73.0 ± 21.3 J mol-1 K-1; and k-1/k2 = 12.0 ± 0.3. Conditional pseudo-first-order rate constant k0 increased linearly with the concentration of NaY, while it decreased drastically with the concentration of NaX. Some plausible mechanisms were examined, and the following mechanism was proposed.>

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    UR - http://www.scopus.com/inward/citedby.url?scp=0032140069&partnerID=8YFLogxK

    M3 - Article

    VL - 30

    SP - 523

    EP - 532

    JO - International Journal of Chemical Kinetics

    JF - International Journal of Chemical Kinetics

    SN - 0538-8066

    IS - 8

    ER -