Metalloradical Cations and Dications Based on Divinyldiphosphene and Divinyldiarsene Ligands |
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| Authors: | Dr. Mahendra K. Sharma Dr. Dennis Rottschäfer Beate Neumann Dr. Hans-Georg Stammler Sergi Danés Dr. Diego M. Andrada Dr. Maurice van Gastel Dr. Alexander Hinz Priv.-Doz. Dr. Rajendra S. Ghadwal |
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| Affiliation: | 1. Molecular Inorganic Chemistry and Catalysis, Inorganic and Structural Chemistry, Center for Molecular Materials, Faculty of Chemistry, Universität Bielefeld, Universitätsstrasse 25, 33615 Bielefeld, Germany;2. Allgemeine und Anorganische Chemie, Universität des Saarlandes, Campus C4.1, 66123 Saarbrücken, Germany;3. Max-Planck-Institut für Kohlenforschung Molecular Theory and Spectroscopy, Kaiser-Wilhelm-Platz 1, Mülheim an der Ruhr, 45470 Germany;4. Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), Engesserstrasse 15, 76131 Karlsruhe, Germany |
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| Abstract: | Metalloradicals are key species in synthesis, catalysis, and bioinorganic chemistry. Herein, two iron radical cation complexes ( 3-E )GaCl4 [( 3-E ).+ = [{(IPr)C(Ph)E}2Fe(CO)3].+, E = P or As; IPr = C{(NDipp)CH}2, Dipp = 2,6-iPr2C6H3] are reported as crystalline solids. Treatment of the divinyldipnictenes {(IPr)C(Ph)E}2 ( 1-E ) with Fe2(CO)9 affords [{(IPr)C(Ph)E}2Fe(CO)3] ( 2-E ), in which 1-E binds to the Fe atom in an allylic (η3-EECvinyl) fashion and functions as a 4e donor ligand. Complexes 2-E undergo 1e oxidation with GaCl3 to yield ( 3-E )GaCl4. Spin density analysis revealed that the unpaired electron in ( 3-E ).+ is mainly located on the Fe (52–64 %) and vinylic C (30–36 %) atoms. Further 1e oxidation of ( 3-E )GaCl4 leads to unprecedented η3-EECvinyl to η3-ECvinylCPh coordination shuttling to form the dications ( 4-E )(GaCl4)2. |
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| Keywords: | arsenic coordination modes iron phosphorus radical ions |
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