Preparation, optical resolution, racemization, and ligand isotopic exchange of tris(1,3-diphenyl-1,3-propanedionato)-germanium(IV) perchlorate in acetonitrile.
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概要
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Tris(1,3-diphenyl-1,3-propanedionato)germanium(IV) [Ge(bzbz)<SUB>3</SUB>]<SUP>+</SUP> was prepared as crystalline perchlorate, and resolved by the crystallization of its salt with hydrogen (<I>R</I>,<I>R</I>)-<I>O</I>,<I>O</I>-dibenzoyltartrate. The patterns of UV and circular dichroism spectra are very similar to those of [Si(bzbz)<SUB>3</SUB>]ClO<SUB>4</SUB>. The racemization of the <I>Δ</I>-[Ge(bzbz)<SUB>3</SUB>]ClO<SUB>4</SUB> was studied kinetically in acetonitrile at 40–60 °C to find the rate law: Rate=<I>k</I><SUB>rac</SUB>[complex], where <I>k</I><SUB>rac</SUB>=9.86×10<SUP>−5</SUP> s<SUP>−1</SUP> at 50 °C. The activation parameters (Δ<I>H</I><SUP>\neweq</SUP>=99±2 kJ mol<SUP>−1</SUP> and Δ<I>S</I><SUP>\neweq</SUP>=−17±2 J K<SUP>−1</SUP> mol<SUP>−1</SUP>) are very similar to those of tris(acetylacetonato)germanium (IV) complex. Compared with the rate of ligand isotopic exchange, the racemization should proceed <I>via</I> intramolecular mechanism. The steric effect coming from the substituents on the chelate ring should play an important role in determining the racemization rate.
- 公益社団法人 日本化学会の論文
著者
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Saito Kazuo
Chemistry Department, Faculty of Science, Tohoku University
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Nagasawa Akira
Chemistry Department, Faculty of Science, Tohoku University
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Ueno Fumio
Chemistry Department, Faculty of Science, Tohoku University
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