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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 11, Number 3
BKCSDE 11(3)
March 20, 1990 

Template Synthesis and Characterization of Four- and Five-Coordinate Copper(Ⅱ) Complexes with Hexaaza Macrotricyclic Ligands 1,3,6,9,11,14-Hexaazatricyclo[,9]octadecane(L1) and 1,3,6,10,12,15-Hexaazatricyclo[,10]eicosane(L2)
Myunghyun Paik Suh*, Shin-Geol Kang, Teak-Mo Chung
Cu(Ⅱ) hexaazamacrotricyclic complexes [Cu(L)](ClO4)2 and [(Cu(L)Cl]ClO4, where L = 1,3,6,9,11,14-hexaazatricyclo[,9]octadeca ne(L1) or 1,3,6,10,12,15-hexaazatricyclo[,10]eicosa ne(L2), have been prepared by the simple template condensation reactions of triamines, diethylenetriamine for L1, and N-(2-aminoethyl)-1,3-propanediamine for L2, with formaldehyde in the presence of Cu(OAc)2 or CuCl2. The Cu(Ⅱ) complexes of L1 contain two 1,3-diazacyclopentane ring moieties and those of L2 contain two 1,3-diazacyclohexane ring moieties that are fused to the 14-membered macrocyclic framework. Spectra indicate that complexes [Cu(L)](ClO4)2 and [Cu(L)Cl]ClO4 have square-planar and square-pyramidal chromophores, respectively. square-planar [Cu(L)](ClO4)2 are remarkably stable against ligand dissociation in acidic aqueous solutions. Square-pyramidal [Cu(L)Cl]ClO4 complexes dissociate their axial Cl-ligands easily in aqueous solutions to form [Cu(L)H2O]2+ species. Infrared and UV/vis absorption spectra of the Cu(Ⅱ) complexes reveal that Cu-N interactions and the ligand field strengths are significantly weaker in the complexes of L2 than in the complexes of L1.
206 - 208
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