J. Phys. IV France 7 (1997) C2-663-C2-664
XAFS Studies of High-Valent Porphyrinato Manganèse Complexes with OzoneV. Gotte1, J. Goulon1, A. Rogalev1, C. Goulon-Ginet1, 2, K. Perié3, J.M. Barbe3, R. Guilard3 and P. Cocolios4
1 ESRF, BP. 220, 38043 Grenoble, France
2 Université Joseph-Fourler, Faculté de Pharmacie, 38706 La Tronche, France
3 LIMSAG (UMR 9953), Université de Bourgogne, 6 boulevard Gabriel, 21100 Dijon, France
4 Centre de Recherche Air Liquide, BP. 126, Les Loges-en-Josas, 78350 Jouy-en-Josas, France
We produce strong evidence of the interaction of ozone with a series of Manganese (III) porphyrinato complexes to form a well defined reactive intermediate. In the latter species, the Manganese atom which is formally in a tetravalent (IV) state, is (at least) hexacoordinated with the metal unambiguously lying in the basal plane of the four pyrrolic nitrogens of the porphyrin macrocycle. Substitution of Bromine or Chlorine axial ligands by ozonids is most likely to happen. This conclusion is also supported by XANES and EXAFS spectra recorded at the Chlorine K-edge which suggest that ozone may even form with chlorine a complex anion.
© EDP Sciences 1997