A kinetic study of the reactions of dimethyl sulfide bridged tetramethylplatinum(II) and octamethylplatinum(IV) complexes with dimethyl sulfide and bidentate ligands

Katsuyuki Nakayama, Yuichi Kondo, Koji Ishihara

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    8 Citations (Scopus)

    Abstract

    Kinetics for the reactions of [1] [PtIV 2Me8 (μ-SMe2)2] + 2 Me2S kfkd 2 [PtIVMe4(SMe2)2] [2] [PtII 2Me4 (μ-SMe2)2] + 2 Me2S kf→ 2 [PtIIMe2(SMe2)2] and [3] [PtIV 2Me8 (μ-SMe2)2] + 2NN → 2 [PtIVMe4(NN)] + 2 Me2S where NN = bipy or 4,4′-Me2-bipy, have been studied at various temperatures and pressures. Reaction [3] was shown to consist of the rapid conversion of the dimer to a monomer and the much slower subsequent substitution of the dimethyl sulfide with bidentate ligand NN: [PtIV 2Me8(μ-SMe2)2] + 2 Me2S ⇌ 2 [PtIVMe4(SMe2)2] and [PtIVMe4(SMe2)2] + NN → [PtIVMe4(NN)] + 2 Me2S The rate constants and activation parameters for the reactions areas follows: kf= 3.16 ± 0.06 M-1 s-1 (25°C), ΔH f = 51.8 ± 1.7 kJ mol-1, ΔS f = -61.0 ± 5.8 J mol-1 K-1, kd= 1.18 ± 0.22 M-1 s-1 (25°C), ΔH d = 65 ± 22 kJ mol-1, ΔS d = -26 ± 73 J mol-1 K-1 for reaction [1] in n-hexane; kf = 6.68 ± 0.06 M-1 s-1 (25°C), ΔH f = 58.0 ± 3.1 kJ mol-1, ΔS f = -34.5 ± 10.5 J mol-1 K-1, ΔV f = -10.7 ± 1.3 cm3 mol-1 for reaction [2] in dichloromethane; k2= (7.09 ± 1.89) × 10-4 M-1 s-1, ΔH 2 = 95 ± 21 kJ mol-1, and ΔS 2 = 18 ± 70 J mol-1 K-1, ΔV 2 = 9 ± 9 cm3 mol-1 for reaction [3] with bipy, and kl = (1.10 ± 0.10) × 10-2 s-1, k3/k-1 = (4.33 ± 0.30) × 10-2, and k2= (6.09 ± 1.35) × 10-4 M-1 s-1 for reaction [3] with 4,4′-Me2-bipy. It was shown that reactions [1] and [2] proceed nucleophilically without any intermediates, and reaction [3] proceeds through a mainly k2 path for NN = bipy and through both k1 and k2 paths for NN = 4,4′-Me2-bipy, without appreciable participation of the direct reaction between the dimer and NN as shown by the following reaction scheme.

    Original languageEnglish
    Pages (from-to)62-70
    Number of pages9
    JournalCanadian Journal of Chemistry
    Volume76
    Issue number1
    Publication statusPublished - 1998

    Fingerprint

    Dimers
    Ligands
    Kinetics
    Methylene Chloride
    Dichloromethane
    Hexane
    Rate constants
    Substitution reactions
    Monomers
    Chemical activation
    Temperature
    Sulfides
    dimethyl sulfide
    n-hexane

    Keywords

    • High-pressure kinetics
    • Octamethylplatinum(IV) dimer
    • Reaction mechanism
    • Tetramethylplatinum(II) dimer

    ASJC Scopus subject areas

    • Chemistry(all)

    Cite this

    @article{bff5a4c9fd1543998757482abafbaf18,
    title = "A kinetic study of the reactions of dimethyl sulfide bridged tetramethylplatinum(II) and octamethylplatinum(IV) complexes with dimethyl sulfide and bidentate ligands",
    abstract = "Kinetics for the reactions of [1] [PtIV 2Me8 (μ-SMe2)2] + 2 Me2S kf⇌kd 2 [PtIVMe4(SMe2)2] [2] [PtII 2Me4 (μ-SMe2)2] + 2 Me2S kf→ 2 [PtIIMe2(SMe2)2] and [3] [PtIV 2Me8 (μ-SMe2)2] + 2NN → 2 [PtIVMe4(NN)] + 2 Me2S where NN = bipy or 4,4′-Me2-bipy, have been studied at various temperatures and pressures. Reaction [3] was shown to consist of the rapid conversion of the dimer to a monomer and the much slower subsequent substitution of the dimethyl sulfide with bidentate ligand NN: [PtIV 2Me8(μ-SMe2)2] + 2 Me2S ⇌ 2 [PtIVMe4(SMe2)2] and [PtIVMe4(SMe2)2] + NN → [PtIVMe4(NN)] + 2 Me2S The rate constants and activation parameters for the reactions areas follows: kf= 3.16 ± 0.06 M-1 s-1 (25°C), ΔH≠ f = 51.8 ± 1.7 kJ mol-1, ΔS≠ f = -61.0 ± 5.8 J mol-1 K-1, kd= 1.18 ± 0.22 M-1 s-1 (25°C), ΔH≠ d = 65 ± 22 kJ mol-1, ΔS≠ d = -26 ± 73 J mol-1 K-1 for reaction [1] in n-hexane; kf = 6.68 ± 0.06 M-1 s-1 (25°C), ΔH≠ f = 58.0 ± 3.1 kJ mol-1, ΔS≠ f = -34.5 ± 10.5 J mol-1 K-1, ΔV≠ f = -10.7 ± 1.3 cm3 mol-1 for reaction [2] in dichloromethane; k2= (7.09 ± 1.89) × 10-4 M-1 s-1, ΔH≠ 2 = 95 ± 21 kJ mol-1, and ΔS≠ 2 = 18 ± 70 J mol-1 K-1, ΔV≠ 2 = 9 ± 9 cm3 mol-1 for reaction [3] with bipy, and kl = (1.10 ± 0.10) × 10-2 s-1, k3/k-1 = (4.33 ± 0.30) × 10-2, and k2= (6.09 ± 1.35) × 10-4 M-1 s-1 for reaction [3] with 4,4′-Me2-bipy. It was shown that reactions [1] and [2] proceed nucleophilically without any intermediates, and reaction [3] proceeds through a mainly k2 path for NN = bipy and through both k1 and k2 paths for NN = 4,4′-Me2-bipy, without appreciable participation of the direct reaction between the dimer and NN as shown by the following reaction scheme.",
    keywords = "High-pressure kinetics, Octamethylplatinum(IV) dimer, Reaction mechanism, Tetramethylplatinum(II) dimer",
    author = "Katsuyuki Nakayama and Yuichi Kondo and Koji Ishihara",
    year = "1998",
    language = "English",
    volume = "76",
    pages = "62--70",
    journal = "Canadian Journal of Chemistry",
    issn = "0008-4042",
    publisher = "National Research Council of Canada",
    number = "1",

    }

    TY - JOUR

    T1 - A kinetic study of the reactions of dimethyl sulfide bridged tetramethylplatinum(II) and octamethylplatinum(IV) complexes with dimethyl sulfide and bidentate ligands

    AU - Nakayama, Katsuyuki

    AU - Kondo, Yuichi

    AU - Ishihara, Koji

    PY - 1998

    Y1 - 1998

    N2 - Kinetics for the reactions of [1] [PtIV 2Me8 (μ-SMe2)2] + 2 Me2S kf⇌kd 2 [PtIVMe4(SMe2)2] [2] [PtII 2Me4 (μ-SMe2)2] + 2 Me2S kf→ 2 [PtIIMe2(SMe2)2] and [3] [PtIV 2Me8 (μ-SMe2)2] + 2NN → 2 [PtIVMe4(NN)] + 2 Me2S where NN = bipy or 4,4′-Me2-bipy, have been studied at various temperatures and pressures. Reaction [3] was shown to consist of the rapid conversion of the dimer to a monomer and the much slower subsequent substitution of the dimethyl sulfide with bidentate ligand NN: [PtIV 2Me8(μ-SMe2)2] + 2 Me2S ⇌ 2 [PtIVMe4(SMe2)2] and [PtIVMe4(SMe2)2] + NN → [PtIVMe4(NN)] + 2 Me2S The rate constants and activation parameters for the reactions areas follows: kf= 3.16 ± 0.06 M-1 s-1 (25°C), ΔH≠ f = 51.8 ± 1.7 kJ mol-1, ΔS≠ f = -61.0 ± 5.8 J mol-1 K-1, kd= 1.18 ± 0.22 M-1 s-1 (25°C), ΔH≠ d = 65 ± 22 kJ mol-1, ΔS≠ d = -26 ± 73 J mol-1 K-1 for reaction [1] in n-hexane; kf = 6.68 ± 0.06 M-1 s-1 (25°C), ΔH≠ f = 58.0 ± 3.1 kJ mol-1, ΔS≠ f = -34.5 ± 10.5 J mol-1 K-1, ΔV≠ f = -10.7 ± 1.3 cm3 mol-1 for reaction [2] in dichloromethane; k2= (7.09 ± 1.89) × 10-4 M-1 s-1, ΔH≠ 2 = 95 ± 21 kJ mol-1, and ΔS≠ 2 = 18 ± 70 J mol-1 K-1, ΔV≠ 2 = 9 ± 9 cm3 mol-1 for reaction [3] with bipy, and kl = (1.10 ± 0.10) × 10-2 s-1, k3/k-1 = (4.33 ± 0.30) × 10-2, and k2= (6.09 ± 1.35) × 10-4 M-1 s-1 for reaction [3] with 4,4′-Me2-bipy. It was shown that reactions [1] and [2] proceed nucleophilically without any intermediates, and reaction [3] proceeds through a mainly k2 path for NN = bipy and through both k1 and k2 paths for NN = 4,4′-Me2-bipy, without appreciable participation of the direct reaction between the dimer and NN as shown by the following reaction scheme.

    AB - Kinetics for the reactions of [1] [PtIV 2Me8 (μ-SMe2)2] + 2 Me2S kf⇌kd 2 [PtIVMe4(SMe2)2] [2] [PtII 2Me4 (μ-SMe2)2] + 2 Me2S kf→ 2 [PtIIMe2(SMe2)2] and [3] [PtIV 2Me8 (μ-SMe2)2] + 2NN → 2 [PtIVMe4(NN)] + 2 Me2S where NN = bipy or 4,4′-Me2-bipy, have been studied at various temperatures and pressures. Reaction [3] was shown to consist of the rapid conversion of the dimer to a monomer and the much slower subsequent substitution of the dimethyl sulfide with bidentate ligand NN: [PtIV 2Me8(μ-SMe2)2] + 2 Me2S ⇌ 2 [PtIVMe4(SMe2)2] and [PtIVMe4(SMe2)2] + NN → [PtIVMe4(NN)] + 2 Me2S The rate constants and activation parameters for the reactions areas follows: kf= 3.16 ± 0.06 M-1 s-1 (25°C), ΔH≠ f = 51.8 ± 1.7 kJ mol-1, ΔS≠ f = -61.0 ± 5.8 J mol-1 K-1, kd= 1.18 ± 0.22 M-1 s-1 (25°C), ΔH≠ d = 65 ± 22 kJ mol-1, ΔS≠ d = -26 ± 73 J mol-1 K-1 for reaction [1] in n-hexane; kf = 6.68 ± 0.06 M-1 s-1 (25°C), ΔH≠ f = 58.0 ± 3.1 kJ mol-1, ΔS≠ f = -34.5 ± 10.5 J mol-1 K-1, ΔV≠ f = -10.7 ± 1.3 cm3 mol-1 for reaction [2] in dichloromethane; k2= (7.09 ± 1.89) × 10-4 M-1 s-1, ΔH≠ 2 = 95 ± 21 kJ mol-1, and ΔS≠ 2 = 18 ± 70 J mol-1 K-1, ΔV≠ 2 = 9 ± 9 cm3 mol-1 for reaction [3] with bipy, and kl = (1.10 ± 0.10) × 10-2 s-1, k3/k-1 = (4.33 ± 0.30) × 10-2, and k2= (6.09 ± 1.35) × 10-4 M-1 s-1 for reaction [3] with 4,4′-Me2-bipy. It was shown that reactions [1] and [2] proceed nucleophilically without any intermediates, and reaction [3] proceeds through a mainly k2 path for NN = bipy and through both k1 and k2 paths for NN = 4,4′-Me2-bipy, without appreciable participation of the direct reaction between the dimer and NN as shown by the following reaction scheme.

    KW - High-pressure kinetics

    KW - Octamethylplatinum(IV) dimer

    KW - Reaction mechanism

    KW - Tetramethylplatinum(II) dimer

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    VL - 76

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