Michele Cesario, Charles Giannotti, Jean Guilhem, Jack Silver and Janusz Zakrzewski
The crystal structures of
[Fe(oep)L2][O3SCF3] and
[Co(oep)L2][ClO4]
[H2oep = 2,3,7,8,12,13,17,18-octaethylporphyrin,
L = [Fe(C5H5)(C4H4
N)] have been determined. The azaferrocene ligands L in both
compounds are seen to be parallel. The axial M–N (azaferrocene)
bonds are longer than those found in analogous imidazole and pyridine
complexes. Rhombic EPR spectra for bis(azaferrocene) complexes of
iron(III) porphyrins are postulated to be a result of steric
interactions of the azaferrocene H2,5 atoms
splitting the degeneracy of the dxz and
dyz orbitals. The Mössbauer spectra of these iron
complexes were recorded and interpreted as evidence for σ bonding of
the azaferrocene nitrogen atom to the porphyrin iron core with little or no
π back bonding from the porphyrinic iron to the N atom. This is in
agreement with the long bond lengths found in the structures. The rhombic
EPR spectra observed are in keeping with a parallel arrangement of the
ligand planes, as are the magnitudes of the Mössbauer quadrupole
splittings. It is shown that the large gz
values of the complexes are not unusual and must relate to long axial bonds
and to steric effects splitting the dxz and
dyz orbitals.