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Synthesis and Characterization of New Polyaza Macrocyclic Nickel(Ⅱ) and Copper(Ⅱ) Complexes Two Nitrile or Imidate Ester Pendant Arms: Metal-Mediated Hydrolysis and Alcoholysis of the Nitrile Groups
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  • Synthesis and Characterization of New Polyaza Macrocyclic Nickel(Ⅱ) and Copper(Ⅱ) Complexes Two Nitrile or Imidate Ester Pendant Arms: Metal-Mediated Hydrolysis and Alcoholysis of the Nitrile Groups
  • Synthesis and Characterization of New Polyaza Macrocyclic Nickel(Ⅱ) and Copper(Ⅱ) Complexes Two Nitrile or Imidate Ester Pendant Arms: Metal-Mediated Hydrolysis and Alcoholysis of the Nitrile Groups
저자명
Kang. Shin-Geol,Song. Jeong-Hoon,Jeong. Jong-Hwa
간행물명
Bulletin of the Korean Chemical Society
권/호정보
2002년|23권 6호|pp.824-829 (6 pages)
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대한화학회
파일정보
정기간행물|ENG|
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이 논문은 한국과학기술정보연구원과 논문 연계를 통해 무료로 제공되는 원문입니다.
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New di-N-cyanomethylated tetraaza macrocycle 2.13-bis(cyanomethyl)-5.16-dimethyl-2,6,13,17-tetraazatricyclo[$16.4.0.0^7.12$]docosane $(L^2)$ has been prepared by the reaction of 3, 14-dimethyl-2,6,13,17-tetraazatricyclo $(L^1)$ with bromoacetonitrile. The square-planar complexes $[ML^2](ClO_4)_2(M=Ni(II)$ or Cu(II) can be prepared by the reaction of $L^2$ with the corresponding metal ion in acetonitrile. The cyanomethyl groups of $[ML^2](ClO_4)_2readily$ react with water to $yield[ML^3](ClO_4)_2$ containing pendant amide groups. The trans-octahedral complexes $[ML^4](ClO_4)_2$, in which two imidate ester groups are coordinated to the metal ion, can be also prepared by the reaction of $[ML^2](ClO_4)_2with$ methanol under mild conditions. The hydrolysis and alcoholysis reactions of $[ML^2](ClO_4)_2are$ promoted by the central metal ion, in spite of the fact that the cyanomethyl group is not involved in intramolecular coordination. The reactions are also promoted by a base such as triethylamine but are retarded by an $acid(HClO_4).Interestingly$, the imidate ester groups of $[ML^4]^2$ are unusually resistant to hydrolysis even in 0.1 M $HCIO_4$ or 0.1 M NaOH aqueous solution. Crystal structure of $[NiL^4](ClO_4)_2shows$ that the Ni-N (pendant imidate ester group) bond is rlatively strong; the Ni-N bond distance is shorter then the Ni-N(tertiary) distance and is similar to the Ni-N (secondary) distance.