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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 23, Number 6
BKCSDE 23(6)
June 20, 2002 

Synthesis and Characterization of New Polyaza Macrocyclic Nikel(Ⅱ) and Copper(Ⅱ)Complexes Containing Two Nitrile or Imidate Ester Pendant Arms:Metal-Mediated Hydrolysis and Alcoholysis of the Nitrile Group
Shin-Geol Kang, Jeonghoon Song, Jong Hwa Jeong
Macrocyclic complexes, Functional pendant arms, Hydrolysis, Alcoholysis, X-Ray structure.
New di-N-cyanomethylated tetraaza macrocycle 2,3-bis (cyanomethlyl)-5, 16- dimethyl-2,6,13,17-tetraazatri-cyclo [] docosane (L2)) has been prepared by the reaction of the reaction of 3,14- dimethyl-2 ,6,13,17-tetraazatri-cyclo [] docosane (L1) with bromoacetonitrile. The square-planar complexes [ML2](ClO4) 2 (M=Ni(Ⅱ) or Cu(Ⅱ)) can be prepared by the reaction of L2 with the corresponding metal ion in acetonitrile. The cyanomethyl groups of [ML2](ClO4)2 readily react with water to yield [ML3](ClO4)2 containing pendant amide groups. The trans-octahetral complexes [ML4](ClO4)2 , in which two imidate ester group are coordinated to the metal ion, can be also prepared by the reacton of [ML2](ClO4)2 with methanol under mild conditions. The hydrolysis and alcoholysis reaction of [ML2](ClO4)2 are promoted by the central metal ion , in spite of the fact that the cyanomethyl group is not invovled in intramolecular coordination. The reactons are also promoted by a base such as triethylamine but are retarded by an acid (HClO4). Interestingly, the imidate ester groups of [ML4]2+ are unusually resistant to hydrolysis even in 0.1 M HClO4 or 0.1M NaOH aqueous soluton. Crystal structure of [NiL4](ClO4)2 show that the Ni-N (pendant imidate ester group) bond is relatively strong; the Ni-N bond distance is shorter then the Ni-N (tertiary) distance and is similar to the Ni-N (secondary) distance.
824 - 828
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