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Crystalline Divinyldiarsene Radical Cations and Dications.

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-iPr2 C6 H3 ) 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 ?-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 75 As (I=3/2) nuclei.

SUBMITTER: Sharma MK 

PROVIDER: S-EPMC6899687 | biostudies-literature | 2019 Dec

REPOSITORIES: biostudies-literature

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Crystalline Divinyldiarsene Radical Cations and Dications.

Sharma Mahendra K MK   Blomeyer Sebastian S   Neumann Beate B   Stammler Hans-Georg HG   van Gastel Maurice M   Hinz Alexander A   Ghadwal Rajendra S RS   Ghadwal Rajendra S RS  

Angewandte Chemie (International ed. in English) 20191023 49

The divinyldiarsene radical cations [{(NHC)C(Ph)}As]<sub>2</sub> (GaCl<sub>4</sub> ) (NHC=IPr: C{(NDipp)CH}<sub>2</sub> 3; SIPr: C{(NDipp)CH<sub>2</sub> }<sub>2</sub> 4; Dipp=2,6-iPr<sub>2</sub> C<sub>6</sub> H<sub>3</sub> ) and dications [{(NHC)C(Ph)}As]<sub>2</sub> (GaCl<sub>4</sub> )<sub>2</sub> (NHC=IPr 5; SIPr 6) are readily accessible as crystalline solids on sequential one-electron oxidation of the corresponding divinyldiarsenes [{(NHC)C(Ph)}As]<sub>2</sub> (NHC=IPr 1; SIPr 2) with GaCl<s  ...[more]

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