Conglomeratic Solid Solutions in trans(N,t-N)-[Co(leucinato)(tren)]I_2 and trans(N,t-N)-[Co(norleucinato or norvalinato)(tren)][ClO_4]_2 [t-N=tertiary amine nitrogen; tren=tris(2-aminoethyl)amine]

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Abstract

Ternary solubility isotherms of <i>trans</i>(<i>N</i>,<i>t</i>-<i>N</i>)-[Co(leu)(tren)]I<sub>2</sub>, <i>trans</i>(<i>N</i>,<i>t</i>-<i>N</i>)-[Co(n-leu)(tren)][ClO<sub>4</sub>]<sub>2</sub>, and <i>trans</i>(<i>N</i>,<i>t</i>-<i>N</i>)-[Co(n-val)(tren)][ClO<sub>4</sub>]<sub>2</sub> [<i>t</i>-<i>N</i> = tertiary amine nitrogen; leu = leucinate(1−), n-leu = norleucinate(1−), n–val = norvalinate(1−), and tren = tris(2-aminoethyl)amine] were determined at 25 °C. Each isotherm consists of two branches of the solubility curve and one eutectic point; the tie lines do not converge to any apex of the pure enantiomers, but diverge widely. These facts mean that the three complexes simultaneously form a conglomerate and a solid solution. X-Ray crystal analyses were carried out for crystals grown from the three racemic aqueous solutions. All of the crystals were isomorphous to each other in spite of having different amino acidates and counter ions. The crystal structures clearly demonstrated the coexistence of <FONT SIZE="-2">D</FONT>-amino acidate and <FONT SIZE="-2">L</FONT>-amino acidate at one site of the crystal lattice, that is, a solid solution. Furthermore, all of the crystals were partially optically active: <FONT SIZE="-2">D</FONT> : <FONT SIZE="-2">L</FONT> = 63 : 37 for leu complex (space group <i>P</i>3<sub>2</sub>), <FONT SIZE="-2">D</FONT> : <FONT SIZE="-2">L</FONT> = 32 : 68 for n-leu one (<i>P</i>3<sub>1</sub>), and <FONT SIZE="-2">D</FONT> : <FONT SIZE="-2">L</FONT> = 44 : 56% for n-val one (<i>P</i>3<sub>1</sub>). Head-to-tail hydrogen bonding contacts, which form spiral chains along the <i>c</i>-axis, were commonly found for these complexes.

Journal

  • Bulletin of the Chemical Society of Japan

    Bulletin of the Chemical Society of Japan 69(5), 1289-1296, 1996-05-15

    The Chemical Society of Japan

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Codes

  • NII Article ID (NAID)
    10008903018
  • NII NACSIS-CAT ID (NCID)
    AA00580132
  • Text Lang
    ENG
  • Article Type
    ART
  • ISSN
    00092673
  • Data Source
    CJP  J-STAGE 
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