Dinuclear CuIIMII complexes of a phenol-based macrocycle with N(amine)2O2 and N(imine)2O2 metal-binding sites: The effect of chloride ligation upon the site selectivity of metal ions

Masami Yonemura, Masaaki Ohba, Kazuhiro Takahashi, Hisashi Okawa, David E. Fenton

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A phenol-based dinucleating macrocycle, L2-, comprising two 2-(N-methyl)aminomethyl-6-iminomethyl-4-bromophenolate moieties combined by a -(CH2)2-chain at the amino nitrogens and by a -(CH2)3-chain at the imino nitrogens and having dissimilar N(amine)2O2 and N(imine)2O2 metal-binding sites sharing the phenolic oxygens, is obtained as the mononuclear CuII complex [Cu(L)]. The 2-propanol adduct, [Cu(L)]·2-PrOH, crystallizes in a triclinic crystal system, space group P1̄ (No. 2) with Z=2, a=11.621(6), b= 14.17(1), c=9.390(4) Å, a=96.59(6), β=107.78(3), γ=103.78(5)°, V=1400(1) Å3. The crystallography reveals that the CuII resides in the N(imine)2O2 site and has a nearly planar geometry. A series of dinuclear CuIIMII complexes CuM(L)Cl2 (M=Mn, Co, Ni, Cu, Zn) are obtained by reacting [Cu(L)] with metal(II) chloride salts. The methanol adduct of the CuNi complex, [CuNi(L)Cl2] · MeOH, crystallizes in a monoclinic crystal system, space group P21/a (No. 14) with Z=4, a= 14.495(4), b=13.034(4), c=14.978(3) Å, β=91.89(2)°, V=2828(1) Å3. The methanol adduct of the CuZn complex, [CuZn(L)Cl2] · MeOH, crystallizes in a monoclinic crystal system, space group P21/a (No. 14) with Z=4, a=14.680(4), b=12.942(3), c=15.149(4) Å, β=91.25(2)°, V=2877(1) Å3. The X-ray crystallography for the two complexes reveal that the CuII ion resides in the N(imine)2O2 site with the MII (NiII or ZnII) ion in the N(amine)2O2 site. In each complex the CuII and MII ions have nearly square-pyramidal geometry with the chloride ion occupying apical positions. Cryomagnetic studies (4.2-300 K) indicate a significant antiferromagnetic interaction within each dinuclear unit except for the case of the CuZn complex.

Original languageEnglish
Pages (from-to)72-79
Number of pages8
JournalInorganica Chimica Acta
Issue number1
Publication statusPublished - Dec 1 1998


All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

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