Preparation, resolution, and absorption and circular dichroism spectra of (Co(en)n{NH2CH2CH2P(CH3)2}3-n)3+ and the related complexes, and the absolute configuration of (+)589-fac-(Co{NH2CH2CH2P(CH3)2}3)3+ determined by X-ray analysis.
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概要
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A series of complexes, [Co(en)<I><SUB>n</SUB></I>{NH<SUB>2</SUB>CH<SUB>2</SUB>CH<SUB>2</SUB>P(CH<SUB>3</SUB>)<SUB>2</SUB>}<SUB>3−<I>n</I></SUB>]<SUP>3+</SUP> (en=ethylenediamine, <I>n</I>=0,1,2) and three bis(ethylenediamine)cobalt(III) complexes of the related ligands, NH<SUB>2</SUB>CH<SUB>2</SUB>CH<SUB>2</SUB>P(C<SUB>6</SUB>H<SUB>5</SUB>)<SUB>2</SUB>, (<I>S</I>)-NH<SUB>2</SUB>CH(CH<SUB>3</SUB>)CH<SUB>2</SUB>P(C<SUB>6</SUB>H<SUB>5</SUB>)<SUB>2</SUB>, and <I>rac</I>-NH<SUB>2</SUB>CH<SUB>2</SUB>CH<SUB>2</SUB>P(C<SUB>4</SUB>H<SUB>9</SUB>)(C<SUB>6</SUB>H<SUB>5</SUB>) were prepared and resolved (or separated) into optical isomers, and their absorption and circular dichroism spectra were recorded. The molecular structure and the absolute configuration of (+)<SUB>589</SUB>-<I>fac</I>-[Co{NH<SUB>2</SUB>CH<SUB>2</SUB>CH<SUB>2</SUB>P(CH<SUB>3</SUB>)<SUB>2</SUB>}<SUB>3</SUB>]Br<SUB>3</SUB>·3H<SUB>2</SUB>O were determined by X-ray analysis. The crystals are lemon-yellow, orthorhombic, <I>a</I>=26.501(8), <I>b</I>=9.573(4), <I>c</I>=10.081(5) Å, space group P2<SUB>1</SUB>2<SUB>1</SUB>2<SUB>1</SUB>, <I>z</I>=4. The Co atom is surrounded by 3P and 3N in the facial manner with the average distances of 2.237 and 2.041 Å, respectively. The absolute configuration of the complex ion is <I>Δ</I>. The chelate rings are puckered and chiral to form a pseudo λ gauche conformation.
- 公益社団法人 日本化学会の論文
著者
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Matsumoto Keiji
Department Of Applied Physics Graduate School Of Engineering Yokohama National University
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Kashiwabara Kazuo
Department Of Chemistry Faculty Of Science Nagoya University
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Kinoshita Isamu
Department Of Chemistry Graduate School Of Science Osaka City University
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Fujita Junnosuke
Department of Chemistry Faculty of Science Osaka University
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