Comparative Spectroscopic Studies of Iron(III) and Manganese(III) Salen Complexes Having a Weakly Coordinating Triflate Axial Ligand

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Author(s)

    • Kurahashi Takuya
    • Institute for Molecular Science, National Institutes of Natural Sciences|Okazaki Institute for Integrative Bioscience, National Institutes of Natural Sciences
    • Fujii Hiroshi
    • Institute for Molecular Science, National Institutes of Natural Sciences|Okazaki Institute for Integrative Bioscience, National Institutes of Natural Sciences

Abstract

We thoroughly compared spectroscopic and magnetic properties of mononuclear iron(III) and manganese(III) complexes with symmetric and nonsymmetrical salen ligands, in order to investigate the relation between spectroscopic properties and electronic structures. Magnetic susceptibility and dual-mode electron paramagnetic resonance data show the assignment of [Fe<sup>III</sup>(salen)(OTf)] and [Mn<sup>III</sup>(salen)(OTf)] as high-spin <i>S</i> = 5/2 and <i>S</i> = 2 electronic configurations, respectively, irrespective of the electron-donating properties and symmetry of the salen ligand. Further insights into electronic structures of central metal are obtained from <sup>2</sup>H NMR spectra of selectively deuterated complexes, in which [Fe<sup>III</sup>(salen)(OTf)] and [Mn<sup>III</sup>(salen)(OTf)] exhibit well-resolved paramagnetic NMR signals of quite different shift patterns, due to the presence or absence of the unpaired electron in the d<sub><I>x</I><sup>2</sup> - <I>y</I><sup>2</sup></sub> orbital expected for <i>S</i> = 5/2 iron(III) or <i>S</i> = 2 manganese(III) centers.

Journal

  • Bulletin of the Chemical Society of Japan

    Bulletin of the Chemical Society of Japan 85(9), 940-947, 2012

    The Chemical Society of Japan

Codes

  • NII Article ID (NAID)
    130004153115
  • Text Lang
    ENG
  • ISSN
    0009-2673
  • Data Source
    J-STAGE 
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