Mössbauer study and molecular orbital calculations on the organo-iron (I, II) electron reservoir sandwiches CpFen+ (η6-C6(CH3)6) (n = 0,1) and related CpFe (cyclohexadienyl) complexes

J.P. Mariot , P. Michaud , S. Lauer , Dominique Astruc , A.X. Trautwein , F. Varret

The paramagnetic Fe(I) electron reservoir sandwich η5-C 5H5Fe(I) η6-C6(Me)6, its oxidized mono-cationic diamagnetic form and related diamagnetic η5-C5H 5Fe (cyclohexadienyl) complexes have been studied by Mössbauer spectroscopy on powders and aligned crystals. Spectra under high magnetic field were recorded for powders. On the basis of X-ray data I.E.H.T. MO calculations were performed and gave results in good agreement with experimental data at room temperature and liquid helium temperature. The relaxation of molecular orbitals associated to the electronic reduction from II to I was found to be negligible, which enables to consider a Fe(I) complex as a superposition of a Fe(II) complex and one electron. This electron is occupying the doubly degenerate e *1 orbital and has a very strong metallic character (83 %).

Mots clés: diamagnetic properties of substances; EHT calculations; iron compounds; Mossbauer effect

Domaines: Articles anciens

J.P. Mariot, P. Michaud, S. Lauer, Dominique Astruc, A.X. Trautwein, et al.. Mössbauer study and molecular orbital calculations on the organo-iron (I, II) electron reservoir sandwiches CpFen+ (η6-C6(CH3)6) (n = 0,1) and related CpFe (cyclohexadienyl) complexes. Journal de Physique, 1983, 44 (12), pp.1377-1385. ⟨10.1051/jphys:0198300440120137700⟩. ⟨jpa-00209725⟩