Crystalline Divinyldiarsene Radical Cations and Dications

Sharma MK, Blomeyer S, Neumann B, Stammler H-G, van Gastel M, Hinz A, Ghadwal RS (2019)
Angewandte Chemie International Edition 58(49): 17599-17603.

Zeitschriftenaufsatz | Veröffentlicht| Englisch
 
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Autor*in
Sharma, Mahendra KumarUniBi; Blomeyer, SebastianUniBi ; Neumann, BeateUniBi; Stammler, Hans-GeorgUniBi; van Gastel, Maurice; Hinz, Alexander; Ghadwal, Rajendra S.
Abstract / Bemerkung
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-iPr(2)C(6)H(3)) 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 pi-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 As-75 (I=3/2) nuclei.
Stichworte
arsenic; dications; main-group compounds; pi ligands; radicals
Erscheinungsjahr
2019
Zeitschriftentitel
Angewandte Chemie International Edition
Band
58
Ausgabe
49
Seite(n)
17599-17603
ISSN
1433-7851
eISSN
1521-3773
Page URI
https://pub.uni-bielefeld.de/record/2939183

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Sharma MK, Blomeyer S, Neumann B, et al. Crystalline Divinyldiarsene Radical Cations and Dications. Angewandte Chemie International Edition. 2019;58(49):17599-17603.
Sharma, M. K., Blomeyer, S., Neumann, B., Stammler, H. - G., van Gastel, M., Hinz, A., & Ghadwal, R. S. (2019). Crystalline Divinyldiarsene Radical Cations and Dications. Angewandte Chemie International Edition, 58(49), 17599-17603. doi:10.1002/anie.201909144
Sharma, M. K., Blomeyer, S., Neumann, B., Stammler, H. - G., van Gastel, M., Hinz, A., and Ghadwal, R. S. (2019). Crystalline Divinyldiarsene Radical Cations and Dications. Angewandte Chemie International Edition 58, 17599-17603.
Sharma, M.K., et al., 2019. Crystalline Divinyldiarsene Radical Cations and Dications. Angewandte Chemie International Edition, 58(49), p 17599-17603.
M.K. Sharma, et al., “Crystalline Divinyldiarsene Radical Cations and Dications”, Angewandte Chemie International Edition, vol. 58, 2019, pp. 17599-17603.
Sharma, M.K., Blomeyer, S., Neumann, B., Stammler, H.-G., van Gastel, M., Hinz, A., Ghadwal, R.S.: Crystalline Divinyldiarsene Radical Cations and Dications. Angewandte Chemie International Edition. 58, 17599-17603 (2019).
Sharma, Mahendra Kumar, Blomeyer, Sebastian, Neumann, Beate, Stammler, Hans-Georg, van Gastel, Maurice, Hinz, Alexander, and Ghadwal, Rajendra S. “Crystalline Divinyldiarsene Radical Cations and Dications”. Angewandte Chemie International Edition 58.49 (2019): 17599-17603.

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