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Synthesis, spectroscopic and structural characterization of the high-spin Fe(II) cyanato-N and thiocyanato-N “picket fence” porphyrin complexes
Authors:Mondher Dhifet  Jean-Claude Daran  Habib Nasri
Institution:a Laboratoire de physico-chimie des matériaux, Faculté des Sciences de Monastir, Avenue de l’Environnement, 5019 Monastir, Tunisia
b Laboratoire de Chimie de Coordination CNRS UPR 8241, 205 Route de Norbone, 31077 Toulouse, Cedex 04, France
c Department of Physics, Knox College, Galesburg, IL 61401, USA
Abstract: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 Mössbauer 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) Å), the distance between the iron and the 24-atom mean plane of the porphyrin ring (Fe-PC = 0.6805(7) Å) and the distance between the iron and the plane made by the four pyrrole nitrogens (Fe-PN = 0.5923(12) Å) 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.
Keywords:Cyanato complex  Thiocyanato complex  Iron(II) porphyrin  Structural studies    ssbauer spectroscopy
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