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A Mixed-Valence Fluorido-Bridged FeIIFeIII Complex

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Bill,  Eckhard
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Citation

Dammers, S., Zimmermann, T. P., Walleck, S., Stammler, A., Boegge, H., Bill, E., et al. (2017). A Mixed-Valence Fluorido-Bridged FeIIFeIII Complex. Inorganic Chemistry, 56(4), 1779-1782. doi:10.1021/acs.inorgchem.6b03093.


Cite as: http://hdl.handle.net/21.11116/0000-0006-E1E6-8
Abstract
The reaction of the new dinucleating ligand susan(6-Me) with Fe(BF4)(2)6H(2)O results in formation of the homovalent (FeFeII)-Fe-II complex [(susan(6-Me)){Fe-II(-F)(2)Fe-II}](2+) and the mixed-valence (FeFeIII)-Fe-II complex [(susan(6-Me)){(FeF)-F-II(-F)(FeF)-F-III}](2+) depending on the absence or presence of dioxygen, respectively. Complex [(susan(6-Me)){(FeF)-F-II(-F)(FeF)-F-III}](2+) is the first molecular mixed-valence complex with a fluorido bridge. The short Fe-III-F bond of 1.87 a causes a large reorganization energy, resulting in a localized class II system with an intervalence charge-transfer band of high energy at 10000 cm(1).