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Template Synthesis and Characterization of Four- and Five-Coordinate Copper(II) Complexes with Hexaaza Macrotricyclic Ligands 1,3,6,9,11,14-Hexaazatricyclo $[12.2.1.1^{6,9}]octadecane(L_1)$ and 1,3,6,10,12,15-Hexaazatricyclo $[13.3.1.1^{6,10}]eicosane(L_1)$

  • Myunghyun Paik Suh (Department of Chemistry Education, Seoul National University) ;
  • Shin-Geol Kang (Department of Chemistry Education, Seoul National University) ;
  • Teak-Mo Chung (Department of Chemistry Education, Seoul National University)
  • Published : 1990.06.20

Abstract

Cu(II) hexaazamacrotricyclic complexes $[Cu(L)](ClO_4)_2$ and $[(Cu(L)Cl]ClO_4$, where L = 1,3,6,9,11,14-hexaazatricyclo$[12.2.1.1^{6,9}]octadecane(L_1)$ or 1,3,6,10,12,15-hexaazatricyclo$[13.3.1.1^{6,10}]eicosane(L_2)$, have been prepared by the simple template condensation reactions of triamines, diethylenetriamine for $L_1$, and N-(2-aminoethyl)-1,3-propanediamine for $L_2$, with formaldehyde in the presence of $Cu(OAc)_2\;or\;CuCl_2$. The Cu(II) complexes of $L_1$ contain two 1,3-diazacyclopentane ring moieties and those of $L_2$ contain two 1,3-diazacyclohexane ring moieties that are fused to the 14-membered macrocyclic framework. Spectra indicate that complexes $[Cu(L)](ClO_4)_2\;and\;[Cu(L)Cl]ClO_4$ have square-planar and square-pyramidal chromophores, respectively. square-planar $[Cu(L)](ClO_4)_2$ are remarkably stable against ligand dissociation in acidic aqueous solutions. Square-pyramidal $[Cu(L)Cl]ClO_4$ complexes dissociate their axial Cl-ligands easily in aqueous solutions to form $[Cu(L)H_2O]^{2+}$ 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 $L_2$ than in the complexes of $L_1$.

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Cited by

  1. Template Synthesis of Copper(II) Complexes of N3O-Donor Macrotricycles Containing N-CH2-N and N-CH2-O Linkages vol.25, pp.12, 1990, https://doi.org/10.5012/bkcs.2004.25.12.1973
  2. Synthesis and Characterization of New Hexaaza Macrotricyclic Copper(II) Complexes with a 5-6-6-6 Chelate Ring Sequence vol.27, pp.4, 1990, https://doi.org/10.5012/bkcs.2006.27.4.577
  3. Metal-Directed Condensation of Two Different Triamines with Formaldehyde: Preparation of Asymmetrical Hexaaza Macrotricyclic Copper(II) Complexes with a 5-6-6-6 Chelate Ring Sequence vol.29, pp.6, 1990, https://doi.org/10.5012/bkcs.2008.29.6.1273
  4. One-Pot Reaction Involving Three Different Amines and Formaldehyde Leading to the Formation of New Hexaaza Macrobicyclic Copper(II) Complexes vol.30, pp.7, 2009, https://doi.org/10.5012/bkcs.2009.30.7.1661