• DOI:10.1021/JA034652+
• Corpus ID: 11410961

A high-frequency and high-field EPR study of new azide and fluoride mononuclear Mn(III) complexes.

@article{Mantel2003AHA,
  title={A high-frequency and high-field EPR study of new azide and fluoride mononuclear Mn(III) complexes.},
  author={Claire Mantel and Alia K Hassan and Jacques P{\'e}caut and Alain Deronzier and Marie‐No{\"e}lle Collomb and Carole Duboc-Toia},
  journal={Journal of the American Chemical Society},
  year={2003},
  volume={125 40},
  pages={
          12337-44
        }
}

• Claire Mantel, Alia K Hassan, +3 authors C. Duboc-Toia
• Published 11 September 2003
• Chemistry
• Journal of the American Chemical Society

The isolation, structural characterization and electronic properties of three new six-coordinated Mn(III) complexes, [Mn(bpea)(F)(3)] (1), [Mn(bpea)(N(3))(3)] (2), and [Mn(terpy)(F)(3)] (3) are reported (bpea = N,N-bis(2-pyridylmethyl)-ethylamine; terpy = 2,2':6',2' '-terpyridine). As for [Mn(terpy)(N(3))(3)] (4) (previously described by Limburg J.; Vrettos J. S.; Crabtree R. H.; Brudvig G. W.; de Paula J. C.; Hassan A.; Barra A-L.; Duboc-Toia C.; Collomb M-N. Inorg. Chem. 2001, 40, 1698), all these complexes exhibit a Jahn-Teller distortion of the octahedron characteristic of high-spin Mn(III) (S = 2). The analysis of the crystallographic data shows an elongation along the tetragonal axis of the octahedron for complexes 1 and 3, while complex 2 presents an unexpected compression. The electronic properties were investigated using a high-field and high-frequency EPR study performed between 5 and 15 K (190-575 GHz). The spin Hamiltonian parameters determined in solid state are in agreement with the geometry of the complexes observed in the crystal structures. A negative D value found for 1 and 3 is related to the elongated tetragonal distortion, whereas the positive D value determined for 2 is in accordance with a compressed octahedron. The high E/D values, in the range of 0.103 to 0.230 for all complexes, are correlated with the highly distorted geometry present around the Mn(III) ion. HF-EPR experiments were also performed on complex 1 in solution and show that the D value is the only spin Hamiltonian parameter which is slightly modified compared to the solid state (D = -3.67 cm(-1) in solid state; D = -3.95 cm(-1) in solution).