Structure of cobalt(III) complexes with (R,R)- and (R,S)-N,N,N',N'-tetrakis(2-aminoethyl)-2,4-pentanediamine and N,N,N',N'-tetrakis(2-aminoethyl)-1,3-propanediamine.
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概要
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Crystal structures of the two isomeric Co(III) complexes with sexidentate ligands, (NH<SUB>2</SUB>CH<SUB>2</SUB>CH<SUB>2</SUB>)<SUB>2</SUB>NC<SUP>*</SUP>H(CH<SUB>3</SUB>)CH<SUB>2</SUB>C<SUP>*</SUP>H(CH<SUB>3</SUB>)N(CH<SUB>2</SUB>CH<SUB>2</SUB>NH<SUB>2</SUB>)<SUB>2</SUB> (hereafter abbreviated as <I>R</I>,<I>R</I>- and <I>R</I>,<I>S</I>-tptn) and of the Co(III) complex with a sexidentate ligand, (NH<SUB>2</SUB>CH<SUB>2</SUB>CH<SUB>2</SUB>)<SUB>2</SUB>NCH<SUB>2</SUB>CH<SUB>2</SUB>CH<SUB>2</SUB>N(CH<SUB>2</SUB>CH<SUB>2</SUB>NH<SUB>2</SUB>)<SUB>2</SUB> (abbreviated as ttn) were determined by an X-ray diffraction method. The crystal data and the final <I>R</I> factors are: (<B>1</B>) [Co(<I>R</I>,<I>R</I>-tptn)](ClO<SUB>4</SUB>)<SUB>3</SUB>·H<SUB>2</SUB>O, tetragonal, P4<SUB>2</SUB>2<SUB>1</SUB>2, <I>a</I>=12.800(1), <I>c</I>=15.312(1) Å, <I>V</I>=2509(1) Å<SUP>3</SUP>, <I>Z</I>=4, <I>R</I>=0.053 for 1627 observed unique reflections, (<B>2</B>) [Co(<I>R</I>,<I>S</I>-tptn)]Cl<SUB>3</SUB>·3H<SUB>2</SUB>O, monoclinic, P2<SUB>1</SUB>⁄<I>a</I>, <I>a</I>=16.778(6), <I>b</I>=14.296(2), <I>c</I>=9.478(4) Å, β=110.99(3)°, <I>V</I>=2123(1) Å<SUP>3</SUP>, <I>Z</I>=4, <I>R</I>=0.045 for 3583 reflections and (<B>3</B>) [Co(ttn)]Br<SUB>3</SUB>·H<SUB>2</SUB>O, trigonal, P\={3}cl, <I>a</I>=14.436(4), <I>c</I>=15.718(9) Å, <I>V</I>=2837(2) Å<SUP>3</SUP>, <I>Z</I>=6, <I>R</I>=0.096 for 1183 reflections. The equatorial preference of the methyl groups in the central six-membered chelate ring formed by Co and 2,4-pentanediamine moiety of <I>R</I>,<I>R</I>- and <I>R</I>,<I>S</I>-tptn has been recognized. In (<B>1</B>) the six-membered chelate ring adopts a twist boat form as in (<B>3</B>) with the two C–CH<SUB>3</SUB> bonds in equatorial positions. In (<B>2</B>) the six-membered chelate ring takes a largely flattened chair form with the two C–CH<SUB>3</SUB> bonds again in equatorial positions. The effect of an elongation of the Co–N bond distance on the energy of the first absorption band was discussed.
- 公益社団法人 日本化学会の論文
著者
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Saito Yoshihiko
Department Of Cardiology Juntendo University School Of Medicine
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Ishii Toshio
Department Of Chemistry Chiba Institute Of Technology
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OHBA SHIGERU
Deparment of Biology, Faculty of Science, Tokyo Metropolitan University
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Ito Masatoki
Department of Chemistry, Faculty of Science and Technology, Keio University
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Fukushi Sachio
Department of Chemistry, Chiba Institute of Technology
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Ishii Toshio
Department of Chemistry, Chiba Institute of Technology
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