Stereochemical properties of copper(II) complexes of (RS)-3-aminohexahydroazepine: Crystal and molecular structures of [(R)-3-aminohexahydroazepine][(S)-3-aminohexahydroazepine]copper(II) diperchlorate, [Cu(R-ahaz)(S-ahaz)](ClO4)2 and related complexes.
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概要
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Orange-red copper(II) complexes of (<I>RS</I>)-3-aminohexahydroazepine (=<I>RS</I>-ahaz), Cu(<I>RS</I>-ahaz)<SUB>2</SUB>X<SUB>2</SUB>·<I>n</I>H<SUB>2</SUB>O (X<SUP>−</SUP>=ClO<SUB>4</SUB><SUP>−</SUP>, BF<SUB>4</SUB><SUP>−</SUP>, NO<SUB>3</SUB><SUP>−</SUP>, Br<SUP>−</SUP>, I<SUP>−</SUP>) were prepared, and the molecular structures of complex <B>1</B> (X<SUP>−</SUP>=ClO<SUB>4</SUB><SUP>−</SUP>; <I>n</I>=0) and complex <B>2</B> (X<SUP>−</SUP>=Br<SUP>−</SUP>; <I>n</I>=2) were determined by the single-crystal X-ray diffraction method. The complex <B>1</B> has centrosymmetry, and the complex cation in <B>1</B> involves a pair of <I>R</I>- and <I>S</I>-ahaz (<I>R</I>- and <I>S</I>-ahaz refer to (<I>R</I>)-and (<I>S</I>)-3-aminohexahydroazepine) and takes a strict four-coordination geometry, so that <B>1</B> is formulated as [Cu(<I>R</I>-ahaz)(<I>S</I>-ahaz)](ClO<SUB>4</SUB>)<SUB>2</SUB>. The complex cation in <B>2</B> resembles closely that of <B>1</B>, and <B>2</B> can be represented as [Cu(<I>R</I>-ahaz)(<I>S</I>-ahaz)]Br<SUB>2</SUB>·2H<SUB>2</SUB>O. The other orange-red complexes of <I>RS</I>-ahaz (X<SUP>−</SUP>=BF<SUB>4</SUB><SUP>−</SUP>, NO<SUB>3</SUB><SUP>−</SUP>, I<SUP>−</SUP>) were concluded to take similar strict four-coordinated structures. Blue-violet hetero-anion complexes Cu(<I>RS</I>-ahaz)<SUB>2</SUB>X(ClO<SUB>4</SUB>) were obtained from complex <B>1</B> and LiX (X<SUP>−</SUP>=Cl<SUP>−</SUP>, Br<SUP>−</SUP>). The crystal structure determination of Cu(<I>RS</I>-ahaz)<SUB>2</SUB>Br(ClO<SUB>4</SUB>) (=complex <B>3</B>) revealed that <B>3</B> involves a pair of enantiomeric five-coordinated cations, [CuBr(<I>R</I>-ahaz)<SUB>2</SUB>]<SUP>+</SUP> and [CuBr(<I>S</I>-ahaz)<SUB>2</SUB>]<SUP>+</SUP>, in the single crystal, whereby the ligand exchange which proceeds during the transformation from <B>1</B> to <B>3</B> is indicated.
- 公益社団法人 日本化学会の論文
著者
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Miyamura Kazuo
Department Of Anesthesiology National Mie Chuo Hospital
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Yoshikawa Sadao
Department Of Applied Chemistry Faculty Of Science And Technology Keio University
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Saburi Masahiko
Department Of Applied Chemistry Saitama Institute Of Technology
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Sakurai Tosio
Faculty of Education, Shinshu University
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Tsuboyama Sei
Institute of Physical and Chemical Research
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Morita Masatoshi
Department of Synthetic Chemistry, Faculty of Engineering, The University of Tokyo
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Tsuboyama Kaoru
Institute of Physical and Chemical Research
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Yamazaki Hiroshi
Institute of Physical and Chemical Research
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