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  Metalloradical Cations and Dications Based on Divinyldiphosphene and Divinyldiarsene Ligands

Sharma, M. K., Rottschäfer, D., Neumann, B., Stammler, H.-G., Danés, S., Andrada, D. M., et al. (2021). Metalloradical Cations and Dications Based on Divinyldiphosphene and Divinyldiarsene Ligands. Chemistry – A European Journal, 27(18), 5803-5809. doi:10.1002/chem.202100213.

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 Creators:
Sharma, Mahendra K.1, Author
Rottschäfer, Dennis1, Author
Neumann, Beate1, Author
Stammler, Hans-Georg1, Author
Danés, Sergi2, Author
Andrada, Diego M.2, Author
van Gastel, Maurice3, Author              
Hinz, Alexander4, Author
Ghadwal, Rajendra S.1, Author
Affiliations:
1Molecular Inorganic Chemistry and Catalysis, Inorganic and Structural Chemistry, Center for Molecular Materials, Faculty of Chemistry, Universität Bielefeld, Universitätsstrasse 25, 33615 Bielefeld, Germany, ou_persistent22              
2Allgemeine und Anorganische Chemie, Universität des Saarlandes, Campus C4.1, 66123 Saarbrücken, Germany, ou_persistent22              
3Research Group van Gastel, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541713              
4Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), Engesserstrasse 15, 76131 Karlsruhe, Germany, ou_persistent22              

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Free keywords: arsenic; coordination modes; iron; phosphorus; radical ions
 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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Language(s): eng - English
 Dates: 2021-01-202021-01-202021-03-26
 Publication Status: Published in print
 Pages: 7
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1002/chem.202100213
 Degree: -

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Title: Chemistry – A European Journal
  Other : Chem. – Eur. J.
  Other : Chem. Eur. J.
Source Genre: Journal
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Publ. Info: Weinheim : Wiley-VCH
Pages: - Volume / Issue: 27 (18) Sequence Number: - Start / End Page: 5803 - 5809 Identifier: ISSN: 0947-6539
CoNE: https://pure.mpg.de/cone/journals/resource/954926979058