Mechanism of Racemization of Octahedral Silicon(IV) Complexes with Various β-Diketones in Organic Solvents

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概要

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• Silicon(IV) complexes of 4 kinds of β-diketonate have been resolved and their racemization has been kinetically studied in 1,1,2,2-tetrachloroethane (TCE) and acetonitrile (AN) at 30 to 80 °C. Ultra-violet absorption spectroscopy and isotopic exchange studies with labelled ligands verified intra-molecular mechanism. A similar rate formula to that for the tris(acetylacetonato)silicon(IV) was obtained: <I>k</I><SUB>0</SUB>=<I>k</I><SUB>1</SUB>+<I>k</I><SUB>2</SUB>[acid or base]. Increase in basicity of the ligand decreases the rate. Introduction of methyl group on the central carbon of the six-membered chelate ring markedly enhanced the racemization. It seems as if the intermediate species with a unidentate ligand tends to take <I>trans</I> form around the C=C axis and retards the recombination, giving rise to bigger <I>k</I> values. Mechanism of acid and base catalysis was also discussed.

• 公益社団法人 日本化学会の論文

著者

• Inoue Tomoaki

  Chemistry Department, Faculty of Science, Tohoku University

関連論文

• Mechanism of Racemization of Octahedral Silicon(IV) Complexes with Various β-Diketones in Organic Solvents

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