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Published Online June 1, 2006
Science DOI: 10.1126/science.1128506

Reports

Submitted on April 10, 2006
Accepted on May 19, 2006

An Octahedral Coordination Complex of Iron(VI)

John F. Berry 1, Eckhard Bill 2, Eberhard Bothe 2, Serena DeBeer George 3, Bernd Mienert 2, Frank Neese 4, Karl Wieghardt 2*

1 Max-Planck-Institut für Bioanorganische Chemie, Stiftstrasse 34-36, D-45470 Mülheim an der Ruhr, Germany; Present address: Department of Chemistry, University of Wisconsin, 1101 University Avenue, Madison, WI 53706, USA.
2 Max-Planck-Institut für Bioanorganische Chemie, Stiftstrasse 34-36, D-45470 Mülheim an der Ruhr, Germany.
3 Stanford Synchrotron Radiation Laboratory, Stanford University, Stanford, CA 94309, USA.
4 Max-Planck-Institut für Bioanorganische Chemie, Stiftstrasse 34-36, D-45470 Mülheim an der Ruhr, Germany; Present address: Institut für Physikalische und Theoretische Chemie, Universität Bonn, D-53115 Bonn, Germany.

* To whom correspondence should be addressed.
Karl Wieghardt , E-mail: wieghardt{at}mpi-muelheim.mpg.de

The hexavalent state is considered to be the highest oxidation level accessible for iron, and has previously been found only in the tetrahedral ferrate dianion, FeO42-. Here we report the photochemical synthesis of another Fe(VI) compound, an octahedrally coordinated dication bearing a terminal nitrido ligand. Mössbauer and X-ray absorption spectra, supported by density functional theory, are consistent with the octahedral structure having an Fe{equiv}N triple bond of 1.57 Ångstroms and a singlet dxy2 ground electronic configuration. The compound is stable at 77 Kelvin and reacts yielding a high-spin Fe(III) species on warming.


THIS ARTICLE HAS BEEN CITED BY OTHER ARTICLES:
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J. T. Lyon, H.-S. Hu, L. Andrews, and J. Li (2007)
PNAS 104, 18919-18924
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Science. ISSN 0036-8075 (print), 1095-9203 (online)