Formation mechanism of head-to-head amidato-bridged acetonylplatinum(III) binuclear complexes - Kinetic evidence for π-coordination of the enol form of a ketone in a ligand substitution reaction

Hiroyuki Fukushima, Hiroki Mori, Moritatsu Arime, Satoshi Iwatsuki, Koji Ishihara, Kazuko Matsumoto

    Research output: Contribution to journalArticle

    6 Citations (Scopus)

    Abstract

    Reactions of head-to-head (HH) α-pyridonato- and pivalamidato-bridged platinum(III) binuclear complexes withacetone were investigated kinetically. The reactions with acetone proceeded slowly to form acetonyl PtIII binuclear complexes in two steps. A mechanism, which involves π-coordination of the enol form of acetone in the first step, followed by the π-β bond conversion in the second step, is proposed. π-Coordination of the enol was strongly supported by kinetic analyses of a ligand substitution reaction involving the pivalamidato-bridged PtIII binuclear complex with (4-hydroxyphenyl)pyruvic acid. Only the enol form was reactive towards the PtIII dimer complex. The enol form of acetone coordinates to the Pt(N2O2) atom in the HH amidato-bridged platinum(III) binuclear complex atfirst, and then the π-coordinated acetone changes to the β-coordinated acetone to form the acetonyl PtIII binuclear complex.

    Original languageEnglish
    Pages (from-to)1930-1936
    Number of pages7
    JournalEuropean Journal of Inorganic Chemistry
    Issue number12
    DOIs
    Publication statusPublished - 2011 Apr

    Fingerprint

    Acetone
    Ketones
    Substitution reactions
    Ligands
    Kinetics
    Platinum
    Pyruvic Acid
    Dimers
    Atoms

    Keywords

    • Enols
    • Platinum
    • Reaction mechanisms

    ASJC Scopus subject areas

    • Inorganic Chemistry

    Cite this

    Formation mechanism of head-to-head amidato-bridged acetonylplatinum(III) binuclear complexes - Kinetic evidence for π-coordination of the enol form of a ketone in a ligand substitution reaction. / Fukushima, Hiroyuki; Mori, Hiroki; Arime, Moritatsu; Iwatsuki, Satoshi; Ishihara, Koji; Matsumoto, Kazuko.

    In: European Journal of Inorganic Chemistry, No. 12, 04.2011, p. 1930-1936.

    Research output: Contribution to journalArticle

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    AU - Mori, Hiroki

    AU - Arime, Moritatsu

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    AU - Ishihara, Koji

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