• 제목/요약/키워드: Pentaaza macrocycle

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Syntheses and Properties of New Nickel(II) Complexes of 14-Membered Pentaaza Macrocyclic Ligands with C-Nitro and N-Alkyl Pendant Arms

  • Kang, Shin-Geol;Choi, Jang-Sik
    • Bulletin of the Korean Chemical Society
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    • 제15권5호
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    • pp.374-378
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    • 1994
  • Square planar nickel(II) complexes with various 1-alkyl derivatives of the 14-membered pentaaza macrocycle 8-methyl-8-nitro-1,3,6,10,13-pentaazacyclotetradecane can be readily prepared by two-step metal template condensation reactions of ethylenediamine, nitroethane, formaldehyde, and appropriate primary alkylamines. In coordinating solvents the nickel (II) complexes form octahedral species containing two axially coordinated solvent molecules and thus show square planar-octahedral equilibrium. The properties of the pentaaza macrocyclic complexes are considerably different from those of the complexes of analogous hexaaza and tetraaza macrocyclic complexes. Synthesis, characterization, and spectroscopic and chemical properties of the new complexes are described.

Template Synthesis of New Nickel(Ⅱ) Comlexes of 14-Membered Pentaaza Macrocyclic Ligands: Effects of C-Alkyl and N-Hydroxyalkyl Pendant Arms on the Solution Behaviors of the Complexes

  • 강신걸;최장식;김성진
    • Bulletin of the Korean Chemical Society
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    • 제16권6호
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    • pp.518-523
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    • 1995
  • New square planar nickel(Ⅱ) complexes with various 1-alkyl (4a-4c) and 1-hydroxyalkyl (4d-4f) derivatives of the 14-membered pentaaza macrocycle 8-ethyl-8-nitro-1,3,6,10,13-pentaazacyclotetradecane have been synthesized by two-step metal template condensation reactions of ethylenediamine, nitroethane, formaldehyde, and appropriate primary amines. The nitro group and/or hydroxyl group of 4a-4f are not directly involved in the coordination. The nickel(Ⅱ) complexes exist in coordinating solvents such as MeCN, Me2SO, and H2O as equilibrium mixtures of the square planar [Ni(L)]2+(L=4a-4f) and octahedral species [Ni(L)S2]2+(S=solvent molecule). Although the ligand field strength and redox potentials of the complexes are not affected by the nature of the substituents, the formation of octahedral species for 4d-4f in MeCN is strongly restricted by the hydroxyl group. Synthesis, characterization, and solution behaviors of the nickel(Ⅱ) complexes are described.