Mechanism of ketone and alcohol formations from alkenes and alkynes on the head-to-head 2-pyridonato-bridged cis-diammineplatinum(III) dinuclear complex

Nami Saeki, Noriko Nakamura, Takayuki Ishibashi, Moritatsu Arime, Hideo Sekiya, Koji Ishihara, Kazuko Matsumoto

    Research output: Contribution to journalArticle

    29 Citations (Scopus)

    Abstract

    Reactions of the head-to-head 2-pyridonato-bridged cis-diammineplatinum(III) dinuclear complex having nonequivalent two platinum atoms, Pt(N2O2) and Pt(N4), with p-styrenesulfonate, 2-methyl-2-propene-1-sulfonate, 4-penten-1-ol, and 4-pentyn-ol were studied kinetically. Under the pseudo first-order reaction conditions that the concentration of the PtIII dinuclear complex is much smaller than that of olefin, a consecutive basically four-step reaction was observed: the olefin π-coordinates preferentially to the Pt(N2O2) in the first step (step 1), followed by the second π-coordination of another olefin molecule to the Pt(N4) (step 2). In the next step (step 3), the nucleophilic attack of water to the coordinated olefin triggers the π-σ bond conversion on the Pt(N2O2), and the second π-bonding olefin molecule on the Pt(N4) is released. Finally, reductive elimination occurs to the alkyl group on the Pt(N2O2) to produce the alkyl compound (step 4). The first water substitution with olefin (step 1) occurs to the diaqua and aquahydroxo forms of the complex, whereas the second substitution (step 2) proceeds either on the coordinated OH-on the Pt(N4) (path a) or on the coordinatively unsaturated five-coordinate intermediate of the Pt(N4) (path b), in addition to the common substitution of H2O (path c). The reactions of p-styrenesulfonate and 2-methyl-2-propene-1-sulfonate proceed through paths b and c, whereas the reactions of 4-penten-1-ol and 4-pentyn-1-ol proceed through paths a and c. This difference reflects the difference of the trans effect and/or trans influence of the π-coordinated olefins on the Pt(N2O2). The pentacoordinate state in path b is employed only by the sulfo-olefins, because these exert stronger trans effect. The steps 3 and 4 reflect the effect of the axial alkyl ligand (R) on the charge localization R-PtIV(N2O2)-PtII (N4))and delocalization (R-PtIII(N2O2)-PtIII (N4)(N4)-OH2); when R is p-styrenesulfonate having an electron withdrawing group, the charge localization in the dimer is less pronounced and the water molecule on the Pt(N4) atom is retained (RPtIII(N2O2)-PtIII (N4)-OH2) in the intermediate state. In both routes, the alkyl group undergoes nucleophilic attack of water, and the oxidized products are released via reductive elimination.

    Original languageEnglish
    Pages (from-to)3605-3616
    Number of pages12
    JournalJournal of the American Chemical Society
    Volume125
    Issue number12
    DOIs
    Publication statusPublished - 2003 Mar 26

    Fingerprint

    Alkynes
    Alkenes
    Ketones
    Olefins
    Alcohols
    Substitution reactions
    Water
    Molecules
    Propylene
    Atoms
    Platinum
    Dimers
    Ligands
    Electrons

    ASJC Scopus subject areas

    • Chemistry(all)

    Cite this

    Mechanism of ketone and alcohol formations from alkenes and alkynes on the head-to-head 2-pyridonato-bridged cis-diammineplatinum(III) dinuclear complex. / Saeki, Nami; Nakamura, Noriko; Ishibashi, Takayuki; Arime, Moritatsu; Sekiya, Hideo; Ishihara, Koji; Matsumoto, Kazuko.

    In: Journal of the American Chemical Society, Vol. 125, No. 12, 26.03.2003, p. 3605-3616.

    Research output: Contribution to journalArticle

    Saeki, Nami ; Nakamura, Noriko ; Ishibashi, Takayuki ; Arime, Moritatsu ; Sekiya, Hideo ; Ishihara, Koji ; Matsumoto, Kazuko. / Mechanism of ketone and alcohol formations from alkenes and alkynes on the head-to-head 2-pyridonato-bridged cis-diammineplatinum(III) dinuclear complex. In: Journal of the American Chemical Society. 2003 ; Vol. 125, No. 12. pp. 3605-3616.
    @article{78a97ae6fd5647b2b1838ea7c097a9bb,
    title = "Mechanism of ketone and alcohol formations from alkenes and alkynes on the head-to-head 2-pyridonato-bridged cis-diammineplatinum(III) dinuclear complex",
    abstract = "Reactions of the head-to-head 2-pyridonato-bridged cis-diammineplatinum(III) dinuclear complex having nonequivalent two platinum atoms, Pt(N2O2) and Pt(N4), with p-styrenesulfonate, 2-methyl-2-propene-1-sulfonate, 4-penten-1-ol, and 4-pentyn-ol were studied kinetically. Under the pseudo first-order reaction conditions that the concentration of the PtIII dinuclear complex is much smaller than that of olefin, a consecutive basically four-step reaction was observed: the olefin π-coordinates preferentially to the Pt(N2O2) in the first step (step 1), followed by the second π-coordination of another olefin molecule to the Pt(N4) (step 2). In the next step (step 3), the nucleophilic attack of water to the coordinated olefin triggers the π-σ bond conversion on the Pt(N2O2), and the second π-bonding olefin molecule on the Pt(N4) is released. Finally, reductive elimination occurs to the alkyl group on the Pt(N2O2) to produce the alkyl compound (step 4). The first water substitution with olefin (step 1) occurs to the diaqua and aquahydroxo forms of the complex, whereas the second substitution (step 2) proceeds either on the coordinated OH-on the Pt(N4) (path a) or on the coordinatively unsaturated five-coordinate intermediate of the Pt(N4) (path b), in addition to the common substitution of H2O (path c). The reactions of p-styrenesulfonate and 2-methyl-2-propene-1-sulfonate proceed through paths b and c, whereas the reactions of 4-penten-1-ol and 4-pentyn-1-ol proceed through paths a and c. This difference reflects the difference of the trans effect and/or trans influence of the π-coordinated olefins on the Pt(N2O2). The pentacoordinate state in path b is employed only by the sulfo-olefins, because these exert stronger trans effect. The steps 3 and 4 reflect the effect of the axial alkyl ligand (R) on the charge localization R-PtIV(N2O2)-PtII (N4))and delocalization (R-PtIII(N2O2)-PtIII (N4)(N4)-OH2); when R is p-styrenesulfonate having an electron withdrawing group, the charge localization in the dimer is less pronounced and the water molecule on the Pt(N4) atom is retained (RPtIII(N2O2)-PtIII (N4)-OH2) in the intermediate state. In both routes, the alkyl group undergoes nucleophilic attack of water, and the oxidized products are released via reductive elimination.",
    author = "Nami Saeki and Noriko Nakamura and Takayuki Ishibashi and Moritatsu Arime and Hideo Sekiya and Koji Ishihara and Kazuko Matsumoto",
    year = "2003",
    month = "3",
    day = "26",
    doi = "10.1021/ja020953s",
    language = "English",
    volume = "125",
    pages = "3605--3616",
    journal = "Journal of the American Chemical Society",
    issn = "0002-7863",
    publisher = "American Chemical Society",
    number = "12",

    }

    TY - JOUR

    T1 - Mechanism of ketone and alcohol formations from alkenes and alkynes on the head-to-head 2-pyridonato-bridged cis-diammineplatinum(III) dinuclear complex

    AU - Saeki, Nami

    AU - Nakamura, Noriko

    AU - Ishibashi, Takayuki

    AU - Arime, Moritatsu

    AU - Sekiya, Hideo

    AU - Ishihara, Koji

    AU - Matsumoto, Kazuko

    PY - 2003/3/26

    Y1 - 2003/3/26

    N2 - Reactions of the head-to-head 2-pyridonato-bridged cis-diammineplatinum(III) dinuclear complex having nonequivalent two platinum atoms, Pt(N2O2) and Pt(N4), with p-styrenesulfonate, 2-methyl-2-propene-1-sulfonate, 4-penten-1-ol, and 4-pentyn-ol were studied kinetically. Under the pseudo first-order reaction conditions that the concentration of the PtIII dinuclear complex is much smaller than that of olefin, a consecutive basically four-step reaction was observed: the olefin π-coordinates preferentially to the Pt(N2O2) in the first step (step 1), followed by the second π-coordination of another olefin molecule to the Pt(N4) (step 2). In the next step (step 3), the nucleophilic attack of water to the coordinated olefin triggers the π-σ bond conversion on the Pt(N2O2), and the second π-bonding olefin molecule on the Pt(N4) is released. Finally, reductive elimination occurs to the alkyl group on the Pt(N2O2) to produce the alkyl compound (step 4). The first water substitution with olefin (step 1) occurs to the diaqua and aquahydroxo forms of the complex, whereas the second substitution (step 2) proceeds either on the coordinated OH-on the Pt(N4) (path a) or on the coordinatively unsaturated five-coordinate intermediate of the Pt(N4) (path b), in addition to the common substitution of H2O (path c). The reactions of p-styrenesulfonate and 2-methyl-2-propene-1-sulfonate proceed through paths b and c, whereas the reactions of 4-penten-1-ol and 4-pentyn-1-ol proceed through paths a and c. This difference reflects the difference of the trans effect and/or trans influence of the π-coordinated olefins on the Pt(N2O2). The pentacoordinate state in path b is employed only by the sulfo-olefins, because these exert stronger trans effect. The steps 3 and 4 reflect the effect of the axial alkyl ligand (R) on the charge localization R-PtIV(N2O2)-PtII (N4))and delocalization (R-PtIII(N2O2)-PtIII (N4)(N4)-OH2); when R is p-styrenesulfonate having an electron withdrawing group, the charge localization in the dimer is less pronounced and the water molecule on the Pt(N4) atom is retained (RPtIII(N2O2)-PtIII (N4)-OH2) in the intermediate state. In both routes, the alkyl group undergoes nucleophilic attack of water, and the oxidized products are released via reductive elimination.

    AB - Reactions of the head-to-head 2-pyridonato-bridged cis-diammineplatinum(III) dinuclear complex having nonequivalent two platinum atoms, Pt(N2O2) and Pt(N4), with p-styrenesulfonate, 2-methyl-2-propene-1-sulfonate, 4-penten-1-ol, and 4-pentyn-ol were studied kinetically. Under the pseudo first-order reaction conditions that the concentration of the PtIII dinuclear complex is much smaller than that of olefin, a consecutive basically four-step reaction was observed: the olefin π-coordinates preferentially to the Pt(N2O2) in the first step (step 1), followed by the second π-coordination of another olefin molecule to the Pt(N4) (step 2). In the next step (step 3), the nucleophilic attack of water to the coordinated olefin triggers the π-σ bond conversion on the Pt(N2O2), and the second π-bonding olefin molecule on the Pt(N4) is released. Finally, reductive elimination occurs to the alkyl group on the Pt(N2O2) to produce the alkyl compound (step 4). The first water substitution with olefin (step 1) occurs to the diaqua and aquahydroxo forms of the complex, whereas the second substitution (step 2) proceeds either on the coordinated OH-on the Pt(N4) (path a) or on the coordinatively unsaturated five-coordinate intermediate of the Pt(N4) (path b), in addition to the common substitution of H2O (path c). The reactions of p-styrenesulfonate and 2-methyl-2-propene-1-sulfonate proceed through paths b and c, whereas the reactions of 4-penten-1-ol and 4-pentyn-1-ol proceed through paths a and c. This difference reflects the difference of the trans effect and/or trans influence of the π-coordinated olefins on the Pt(N2O2). The pentacoordinate state in path b is employed only by the sulfo-olefins, because these exert stronger trans effect. The steps 3 and 4 reflect the effect of the axial alkyl ligand (R) on the charge localization R-PtIV(N2O2)-PtII (N4))and delocalization (R-PtIII(N2O2)-PtIII (N4)(N4)-OH2); when R is p-styrenesulfonate having an electron withdrawing group, the charge localization in the dimer is less pronounced and the water molecule on the Pt(N4) atom is retained (RPtIII(N2O2)-PtIII (N4)-OH2) in the intermediate state. In both routes, the alkyl group undergoes nucleophilic attack of water, and the oxidized products are released via reductive elimination.

    UR - http://www.scopus.com/inward/record.url?scp=0037467383&partnerID=8YFLogxK

    UR - http://www.scopus.com/inward/citedby.url?scp=0037467383&partnerID=8YFLogxK

    U2 - 10.1021/ja020953s

    DO - 10.1021/ja020953s

    M3 - Article

    C2 - 12643723

    AN - SCOPUS:0037467383

    VL - 125

    SP - 3605

    EP - 3616

    JO - Journal of the American Chemical Society

    JF - Journal of the American Chemical Society

    SN - 0002-7863

    IS - 12

    ER -