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  Crystalline Divinyldiarsene Radical Cations and Dications

Sharma, M. K., Blomeyer, S., Neumann, B., Stammler, H.-G., van Gastel, M., Hinz, A., et al. (2019). Crystalline Divinyldiarsene Radical Cations and Dications. Angewandte Chemie, International Edition, 58(49), 17599-17603. doi:10.1002/anie.201909144.

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 Creators:
Sharma, Mahendra K.1, Author
Blomeyer, Sebastian1, Author
Neumann, Beate1, Author
Stammler, Hans-Georg1, Author
van Gastel, Maurice2, Author              
Hinz, Alexander3, Author
Ghadwal, Rajendra S.1, Author
Affiliations:
1Anorganische Molekülchemie und Katalyse, Lehrstuhl für Anorganische Chemie und Strukturchemie, Centrum für Molekulare Materialien, Fakultät für Chemie, Universität Bielefeld, Universitätsstr. 25, 33615 Bielefeld, Germany, ou_persistent22              
2Research Group van Gastel, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541713              
3Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), Engesserstr. 15, 76131 Karlsruhe, Germany, ou_persistent22              

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Free keywords: arsenic; dications; main-group compounds; π ligands; radicals
 Abstract: The divinyldiarsene radical cations [{(NHC)C(Ph)}As]2(GaCl4) (NHC=IPr: C{(NDipp)CH}2 3; SIPr: C{(NDipp)CH2}2 4; Dipp=2,6‐iPr2C6H3) and dications [{(NHC)C(Ph)}As]2(GaCl4)2 (NHC=IPr 5; SIPr 6) are readily accessible as crystalline solids on sequential one‐electron oxidation of the corresponding divinyldiarsenes [{(NHC)C(Ph)}As]2 (NHC=IPr 1; SIPr 2) with GaCl3. Compounds 3–6 have been characterized by X‐ray diffraction, cyclic voltammetry, EPR/NMR spectroscopy, and UV/vis absorption spectroscopy as well as DFT calculations. The sequential removal of one electron from the HOMO, that is mainly the As−As π‐bond, of 1 and 2 leads to successive elongation of the As=As bond and contraction of the C−As bonds from 1/2→3/4→5/6. The UV/vis spectrum of 3 and 4 each exhibits a strong absorption in the visible region associated with SOMO‐related transitions. The EPR spectrum of 3 and 4 each shows a broadened septet owing to coupling of the unpaired electron with two 75As (I=3/2) nuclei.

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Language(s): eng - English
 Dates: 2019-07-222019-09-252019-12-02
 Publication Status: Published in print
 Pages: 5
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1002/anie.201909144
 Degree: -

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Title: Angewandte Chemie, International Edition
  Abbreviation : Angew. Chem., Int. Ed.
Source Genre: Journal
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Publ. Info: Weinheim : Wiley-VCH
Pages: - Volume / Issue: 58 (49) Sequence Number: - Start / End Page: 17599 - 17603 Identifier: ISSN: 1433-7851
CoNE: https://pure.mpg.de/cone/journals/resource/1433-7851