Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Synthesis, Crystal structure, and Magnetic Properties of Dinuclear Iron(III) Complexes with Methoxo Bridges

  • Shin, Jong-Won (Department of Chemistry, Kyungpook National University) ;
  • Han, Jeong-Hyeong (Department of Chemistry Education, Kyungpook National University) ;
  • Rowthu, Sankara Rao (Department of Chemistry, Kyungpook National University) ;
  • Kim, Bong-Gon (Department of Chemistry Education, Gyeongsang National University) ;
  • Min, Kil-Sik (Department of Chemistry Education, Kyungpook National University)
  • Received : 2010.08.27
  • Accepted : 2010.10.04
  • Published : 2010.12.20
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Abstract

The reaction of stoichiometric amount of $FeCl_2{\cdot}4H_2O$, (2-pyridylmethyl, 3-pyridylmethyl)amine (2,3-pyma) and sodium azide/sodium thiocyanate in methanol under aerobic conditions affords the dinuclear Fe(III) complexes, [(2,3-pyma) $(N_3)_2Fe({\mu}-OCH_3)_2Fe(N_3)_2$(2,3-pyma)]${\cdot}CH_3OH$ (1) and [(2,3-pyma)$(NCS)_2Fe({\mu}-OCH_3)_2Fe(NCS)_2$(2,3-pyma)] (2) in good yield. Two bis-methoxy-bridged diiron(III) complexes are isolated and characterized. The coordination geometries around iron(III) ions in 1 and 2 are the same tetragonally distorted octahedron. The iron(III) ions are coordinated by two nitrogens of a 2,3-pyma, two nitrogens of two azide/thiocyanate ions, and two oxygens of two methoxy groups. Both compounds are isomorphous. The structures of 1 and 2 display the C-$H{\cdots}\pi$ and/or $\pi-\pi$ stacking interactions as well as hydrogen bonding interactions, respectively. Compounds 1 and 2 show significant antiferromagnetic couplings through the bridged methoxy groups between the iron(III) ions in the temperature range from 5 to 300 K ($H=-2JS_1{\cdot}S_2$, J=-19.1 and $-13.9\;cm^{-1}$ for 1 and 2).

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