Chem. J. Chinese Universities ›› 1998, Vol. 19 ›› Issue (5): 676.

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Synthesis of Linear Oxa-aza Ligands and Formation of Their Copper(Ⅱ) and Zinc(Ⅱ) Complexes

XIE Yong-Shu, KOU Fu-Ping, LIN Rui-Sen, ZONG Han-Xing   

  1. Department of Chemistry, Zhejiang University, Hangzhou, 310027
  • Received:1997-06-07 Online:1998-05-24 Published:1998-05-24

Abstract: Four linear oxa-aza ligands, N, N ′-bis-(2-hydroxyethyl)-ethylenediamine(L1), N-(2-hydroxybenzyl)-3-amino-1-propanol(HL2), N-(2-hydroxyethyl)-N ′-(2-hydroxy-benzyl)-ethylenediamine(HL3) and N-(2-hydroxyethyl) diethylenetriamine(L4), have been synthesized and characterized by elemental analyses, IR and 1H NMR. At (25±0.1) ℃, I=0.10(KNO3), complexation constants of Cu(Ⅱ) with L1 and HL2, and Zn(Ⅱ) with HL3 and L4 were determined by potentiometric pH-titration method. The results indicate that Cu(Ⅱ) forms four coordinated complexes with both L1 and HL2. Alkoxyl groups coordinate at the third coordination sites, with pKa1 values of 7.28 for L1 and 7.32 for HL2 to become alkoxide anions. While at the fourth sites were another alkoxyl or a water molecule with pKa2 values of 9.33 and 9.04 for L1 and HL2, respectively. Zn(Ⅱ) ions form five coordinated complexes with both HL3 and L4. The alkoxyl groups coordinate at the fourth sites with pKa1 values of 7.76 and 7.96. Water molecules at the fifth sites have pKa2 values of 9.47 and 9.57. From the above results, it can be seen that all these complexes yield nucleophiles Cu(Ⅱ)-…ORor Zn(Ⅱ)-…OR at neutral pH, and therefore fit the demand of double-catalysis for ester hydrolysis.

Key words: Unsymmetrical oxa-aza ligands, Copper(Ⅱ) complexes, Zinc(Ⅱ) complexes, Nuleophiles

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