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Crystalline Divinyldiarsene Radical Cations and Dications

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van Gastel,  Maurice
Research Group van Gastel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

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.


Cite as: https://hdl.handle.net/21.11116/0000-0005-4277-B
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.