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 1

Keywords

  • Enols
  • Platinum
  • Reaction mechanisms

ASJC Scopus subject areas

  • Inorganic Chemistry

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