Spectroscopic and structural investigations of the ferrous and ferric high-spin state of a “picket—fence” porphyrinato acetato iron complex. A refined model for the P460 center of hydroxylamine oxidoreductase |
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Authors: | E Bill E L Bominaar X -O Ding J Fischer A Gismelseed H Nasri A X Trautwein R Weiss H Winkler |
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Institution: | 1. Institut für Physik, Medizinische Universit?t, Ratzeburger Allee 160, D-2400, Lübeck, Germany 2. Laboratoire de Cristallochimie de Chimie Structurale, URA (CNRS) 424, Institut Le Bel, Université Louis Pasteur, 4 Rue B. Pascal, F67070, Strasbourg, France
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Abstract: | Mössbauer investigations were performed in the ferrous and ferric form of the ‘picket-fence’ porphyrinato acetato iron complex |Fe(CH3CO2) (TPpivP)|1?,0 at temperatures varying from 1.5–200K and in fields of 0–6.2T. The ferrous complex has an unusually large quadrupole splitting, ΔEQ=+4.25mms?1. The quadrupole splitting in the ferric species, ΔEQ=+1.1mms?1, is as normally found in ferric high-spin iron porphyrins. Spin-Hamiltonian analysis of the magnetic spectra yields zero-field parameters D=?0.9mms?1, E/D=0.33 and magnetic hyperfine parameters Ax,y=?17T, Az=?13.3T in the ferrous high-spin (S=2) complex, and D=7.5cm?1, E/D≈0 and Ax,y,z=20T in the ferric high-spin (S=5/2) species. |
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