Mechanism of the Axial Ligand Substitution Reactions on the Head-to-Tail α-Pyridonato-Bridged cis-Diammineplatinum(III) Dinuclear Complex with Olefins

Moritatsu Arime, Koji Ishihara, Kazuko Matsumoto

    Research output: Contribution to journalArticle

    17 Citations (Scopus)

    Abstract

    Reactions of the head-to-tail α-pyridonato-bridged cis-diammineplatinum(III) dinuclear complex having equivalent two platinum atoms, Pt(N3O), with p-styrenesulfonate and 4-penten-1-ol were studied kinetically. Under the pseudo first-order reaction conditions in which the concentration of the PtIII dinuclear complex is much smaller than that of olefin, a consecutive basically four-step reaction was observed for the reaction with p-styrenesulfonate, but for the reaction with 4-penten-1-ol, the reaction was three step. The olefin π-coordinates to one of the two equivalent Pt atoms in the first step (step 1), followed by the second π-coordination of another olefin molecule to the other Pt atom (step 2). In the next step (step 3), the nucleophilic attack of water to the first π-coordinated olefin initiates its π-σ bond conversion on the Pt atom, and the second π-bonding olefin molecule on the other Pt atom is released. Finally, dissociation of the alkyl group on the Pt(N3O) and reduction of the PtIII dinuclear complex to the PtII dinuclear complex occur (step 4). The first water substitution with olefin (step 1) consists of two paths, the reaction of the diaqua dimer complex (path a) and the reaction of the aquahydroxo dimer complex (path b), whereas the second substitution (step 2) proceeds through three reaction paths: the normal path of the direct substitution of H2O (path c), the path of the coordinated OH- substitution (path d), and the path via the coordinatively unsaturated five-coordinate intermediate (path e). The reaction with p-styrenesulfonate proceeds through paths c, d, and e, whereas the reaction with 4-penten-1-ol proceeds through paths c and d. The third step (step 3) for the reaction with p-styrenesulfonate involves the coordinatively unsaturated intermediate, but that for the 4-pentene reaction does not. The reactivities of the HH dimer and HT dimer with olefins are compared and discussed.

    Original languageEnglish
    Pages (from-to)309-316
    Number of pages8
    JournalInorganic Chemistry
    Volume43
    Issue number1
    DOIs
    Publication statusPublished - 2004 Jan 12

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    Alkenes
    alkenes
    Substitution reactions
    substitutes
    Ligands
    ligands
    Dimers
    Atoms
    dimers
    atoms
    Molecules
    Water
    Platinum
    water
    attack
    molecules
    platinum
    reactivity
    dissociation

    ASJC Scopus subject areas

    • Inorganic Chemistry

    Cite this

    Mechanism of the Axial Ligand Substitution Reactions on the Head-to-Tail α-Pyridonato-Bridged cis-Diammineplatinum(III) Dinuclear Complex with Olefins. / Arime, Moritatsu; Ishihara, Koji; Matsumoto, Kazuko.

    In: Inorganic Chemistry, Vol. 43, No. 1, 12.01.2004, p. 309-316.

    Research output: Contribution to journalArticle

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    abstract = "Reactions of the head-to-tail α-pyridonato-bridged cis-diammineplatinum(III) dinuclear complex having equivalent two platinum atoms, Pt(N3O), with p-styrenesulfonate and 4-penten-1-ol were studied kinetically. Under the pseudo first-order reaction conditions in which the concentration of the PtIII dinuclear complex is much smaller than that of olefin, a consecutive basically four-step reaction was observed for the reaction with p-styrenesulfonate, but for the reaction with 4-penten-1-ol, the reaction was three step. The olefin π-coordinates to one of the two equivalent Pt atoms in the first step (step 1), followed by the second π-coordination of another olefin molecule to the other Pt atom (step 2). In the next step (step 3), the nucleophilic attack of water to the first π-coordinated olefin initiates its π-σ bond conversion on the Pt atom, and the second π-bonding olefin molecule on the other Pt atom is released. Finally, dissociation of the alkyl group on the Pt(N3O) and reduction of the PtIII dinuclear complex to the PtII dinuclear complex occur (step 4). The first water substitution with olefin (step 1) consists of two paths, the reaction of the diaqua dimer complex (path a) and the reaction of the aquahydroxo dimer complex (path b), whereas the second substitution (step 2) proceeds through three reaction paths: the normal path of the direct substitution of H2O (path c), the path of the coordinated OH- substitution (path d), and the path via the coordinatively unsaturated five-coordinate intermediate (path e). The reaction with p-styrenesulfonate proceeds through paths c, d, and e, whereas the reaction with 4-penten-1-ol proceeds through paths c and d. The third step (step 3) for the reaction with p-styrenesulfonate involves the coordinatively unsaturated intermediate, but that for the 4-pentene reaction does not. The reactivities of the HH dimer and HT dimer with olefins are compared and discussed.",
    author = "Moritatsu Arime and Koji Ishihara and Kazuko Matsumoto",
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    N2 - Reactions of the head-to-tail α-pyridonato-bridged cis-diammineplatinum(III) dinuclear complex having equivalent two platinum atoms, Pt(N3O), with p-styrenesulfonate and 4-penten-1-ol were studied kinetically. Under the pseudo first-order reaction conditions in which the concentration of the PtIII dinuclear complex is much smaller than that of olefin, a consecutive basically four-step reaction was observed for the reaction with p-styrenesulfonate, but for the reaction with 4-penten-1-ol, the reaction was three step. The olefin π-coordinates to one of the two equivalent Pt atoms in the first step (step 1), followed by the second π-coordination of another olefin molecule to the other Pt atom (step 2). In the next step (step 3), the nucleophilic attack of water to the first π-coordinated olefin initiates its π-σ bond conversion on the Pt atom, and the second π-bonding olefin molecule on the other Pt atom is released. Finally, dissociation of the alkyl group on the Pt(N3O) and reduction of the PtIII dinuclear complex to the PtII dinuclear complex occur (step 4). The first water substitution with olefin (step 1) consists of two paths, the reaction of the diaqua dimer complex (path a) and the reaction of the aquahydroxo dimer complex (path b), whereas the second substitution (step 2) proceeds through three reaction paths: the normal path of the direct substitution of H2O (path c), the path of the coordinated OH- substitution (path d), and the path via the coordinatively unsaturated five-coordinate intermediate (path e). The reaction with p-styrenesulfonate proceeds through paths c, d, and e, whereas the reaction with 4-penten-1-ol proceeds through paths c and d. The third step (step 3) for the reaction with p-styrenesulfonate involves the coordinatively unsaturated intermediate, but that for the 4-pentene reaction does not. The reactivities of the HH dimer and HT dimer with olefins are compared and discussed.

    AB - Reactions of the head-to-tail α-pyridonato-bridged cis-diammineplatinum(III) dinuclear complex having equivalent two platinum atoms, Pt(N3O), with p-styrenesulfonate and 4-penten-1-ol were studied kinetically. Under the pseudo first-order reaction conditions in which the concentration of the PtIII dinuclear complex is much smaller than that of olefin, a consecutive basically four-step reaction was observed for the reaction with p-styrenesulfonate, but for the reaction with 4-penten-1-ol, the reaction was three step. The olefin π-coordinates to one of the two equivalent Pt atoms in the first step (step 1), followed by the second π-coordination of another olefin molecule to the other Pt atom (step 2). In the next step (step 3), the nucleophilic attack of water to the first π-coordinated olefin initiates its π-σ bond conversion on the Pt atom, and the second π-bonding olefin molecule on the other Pt atom is released. Finally, dissociation of the alkyl group on the Pt(N3O) and reduction of the PtIII dinuclear complex to the PtII dinuclear complex occur (step 4). The first water substitution with olefin (step 1) consists of two paths, the reaction of the diaqua dimer complex (path a) and the reaction of the aquahydroxo dimer complex (path b), whereas the second substitution (step 2) proceeds through three reaction paths: the normal path of the direct substitution of H2O (path c), the path of the coordinated OH- substitution (path d), and the path via the coordinatively unsaturated five-coordinate intermediate (path e). The reaction with p-styrenesulfonate proceeds through paths c, d, and e, whereas the reaction with 4-penten-1-ol proceeds through paths c and d. The third step (step 3) for the reaction with p-styrenesulfonate involves the coordinatively unsaturated intermediate, but that for the 4-pentene reaction does not. The reactivities of the HH dimer and HT dimer with olefins are compared and discussed.

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