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Electronic Structure of Oxo-Bridged Iron(III) Dimers

Schugar, Harvey J. and Rossman, George R. and Barraclough, Colin G. and Gray, Harry B. (1972) Electronic Structure of Oxo-Bridged Iron(III) Dimers. Journal of the American Chemical Society, 94 (8). pp. 2683-2690. ISSN 0002-7863. http://resolver.caltech.edu/CaltechAUTHORS:20131126-152704891

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Abstract

Magnetic susceptibility results and extensive electronic, infrared, and Mi:issbauer spectral data are presented for enH_2[(FeHEDT A)_2O]· 6H_2O_3, Na_4[(FeEDTA)_2O]· 12H_2O, FeHEDTA· H_2O, and NaFeEDT A· 3H_2O (HEDTA = N-hydroxoethylethylenediaminetriacetate, EDTA = ethylenediaminetetraacetate, and enH_2^(2+) = ethylenediammonium cation). The magnetic and spectral data establish an electronic structural model for the oxo-bridged dimers in which pairs of S = 5/2 Fe(III) ions interact antiferromagnetically, with J ≃ -95 cm^(-1). The oxo-bridged dimers show marked intensity enhancement of the one-center Fe(III) ligand-field bands. There are also several uv bands which are interpreted as arising from simultaneous electronic excitations of Fe(III) pairs. A simple high-spin ligand-field model modified by spin-spin interaction is judged to be considerably more appropriate than the Dunitz-Orgel molecular orbital approach as a vehicle for describing oxo-bridged Fe(IIl) dimers.


Item Type:Article
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http://dx.doi.org/10.1021/ja00763a022DOIArticle
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Additional Information:© 1972 American Chemical Society. Received June 24, 1971. Research at Rutgers University was supported by the Rutgers Research Council and a Petroleum Research Fund Starter Grant. Research at the California Institute of Technology was supported by the National Science Foundation. The authors wish to thank Professor R. Herber for obtaining the Mössbauer data and Professor J. Potenza for performing the X-ray diffraction studies related to the singlecrystal spectral measurements. We are also grateful to Professors R. L. Martin and S. J. Lippard for several stimulating discussions regarding the interpretation of various structural, spectral, and magnetic data for oxo-bridged dimeric complexes.
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Rutgers Research CouncilUNSPECIFIED
Petroleum Research Fund Starter GrantUNSPECIFIED
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Record Number:CaltechAUTHORS:20131126-152704891
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20131126-152704891
Official Citation: Electronic structure of oxo-bridge iron(III) dimers Harvey J. Schugar, George R. Rossman, Colin G. Barraclough, and Harry B. Gray Journal of the American Chemical Society 1972 94 (8), 2683-2690
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:42744
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:27 Nov 2013 22:36
Last Modified:27 Nov 2013 22:36

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