Isomerization and Racemization of the Tris(4,4'-dimethyl-2,2'-bipyridine N,N'-dioxide)chromium(III) Complex.

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概要

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• A new chromium(III) complex, [Cr(4,4′-Me<SUB>2</SUB>bpdo)<SUB>3</SUB>]<SUP>3+</SUP> (4,4′-Me<SUB>2</SUB>bpdo=4,4′-dimethyl-2,2′-bipyridine <I>N</I>,<I>N</I>′-dioxide) was prepared and resolved into a pair of enantiomers by an SP-Sephadex column chromatographic method using an achiral eluting agent Na<SUB>2</SUB>SO<SUB>4</SUB>. Both perchlorate and nitrate of the complex were found to crystallize in the <I>lel</I><SUB>2</SUB>·<I>ob</I>(<I>Δ</I>(λλδ), <I>Λ</I>(δδλ)), form. Upon dissolution in water, the complexes isomerized to the <I>lel</I><SUB>3</SUB>(<I>Δ</I>(λλλ), <I>Λ</I>(δδδ)), form with a rapid change in absorption spectra, and then racemized (<I>Δ</I>\rightleftarrows<I>Λ</I>) slowly. The rate constants at 35.0°C were 4.39×10<SUP>−3</SUP> s<SUP>−1</SUP> for the isomerization and 3.46×10<SUP>−5</SUP> s<SUP>−1</SUP> for the racemization. These inversion reactions including conformational change (δ\rightleftarrowsλ) and configurational change (<I>Δ</I>\rightleftarrows<I>Λ</I>) are supposed to proceed by intramolecular mechanisms. The rates of isomerization and racemizatioin of the 4,4′-Me<SUB>2</SUB>bpdo complex are ca. two and ten times slower than those of [Cr(bpdo)<SUB>3</SUB>]<SUP>3+</SUP> (bpdo=2,2′-bipyridine <I>N</I>,<I>N</I>′-dioxide), respectively.

• 公益社団法人 日本化学会の論文

著者

• Kanno Hideaki

  Department Of Chemistry Faculty Of Science Shizuoka University

• Utsuno Shunji

  Department Of Chemistry Faculty Of Science Shizuoka University

• Yamamoto Junko

  Department Of Chemistry Faculty Of Science Shizuoka University

• Fujita Junnosuke

  Department of Chemistry Faculty of Science Osaka University

• Murahashi Satoshi

  Department of Chemistry, Faculty of Science, Shizuoka University

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