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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
Author(s) -
Fukushima Hiroyuki,
Mori Hiroki,
Arime Moritatsu,
Iwatsuki Satoshi,
Ishihara Koji,
Matsumoto Kazuko
Publication year - 2011
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201001089
Subject(s) - chemistry , enol , ligand (biochemistry) , ketone , dimer , acetone , substitution reaction , reaction mechanism , photochemistry , platinum , stereochemistry , medicinal chemistry , catalysis , organic chemistry , biochemistry , receptor
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 Pt III 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–σ 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 Pt III binuclear complex with (4‐hydroxyphenyl)pyruvic acid. Only the enol form was reactive towards the Pt III dimer complex.