Inorganica Chimica Acta p. 3208 - 3213 (2010)
Update date:2022-07-29
Topics: IR spectroscopy NMR spectroscopy Mass spectrometry X-ray crystallography UV-Vis Spectroscopy EPR Spectroscopy
Dhifet, Mondher
Belkhiria, Mohamed Salah
Daran, Jean-Claude
Schulz, Charles E.
Nasri, Habib
Two new iron(II) five-coordinated porphyrin complexes [Na(2,2,2-crypt)] [FeII(TpivPP)(NCO)] (1) (TpivPP = α,α,α,α- tetrakis(o-pivalamidophenyl) porphyrin known as picket fence porphyrin and 2,2,2-crypt is the cryptand-222) and [K(2,2,2-crypt)][FeII(TpivPP) (NCS)] (2) have been prepared and characterized. The UV-Vis and IR spectroscopic data are consistent with a cyanato-N and thiocyanato-N ferrous porphyrinates. The Mo?ssbauer data and the X-ray structural analysis indicate that the Fe(II) cation in 1 and 2 is high-spin (S = 2) and has the (dxy)2(dxz)1(dyz) 1(dz2)1(dx2-y2)1 ground state electronic configuration. For complex 1, the average equatorial iron-pyrrole N bond length (Fe-Np = 2.120(2) ), the distance between the iron and the 24-atom mean plane of the porphyrin ring (Fe-PC = 0.6805(7) ) and the distance between the iron and the plane made by the four pyrrole nitrogens (Fe-PN = 0.5923(12) ) are longer than those of complex 2 and similar five-coordinated Fe(II) high-spin porphyrinates. This is probably due to the significant electronic repulsion of the dx2-y2 and dxy orbitals by the negative charge of the pyrrole N atoms in case of 1.
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