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. 2019 Jun 21;25(35):8249-8253.
doi: 10.1002/chem.201901857. Epub 2019 May 20.

Crystalline Divinyldiarsenes and Cleavage of the As=As Bond

Mahendra K Sharma  1 , Sebastian Blomeyer  1 , Beate Neumann  1 , Hans-Georg Stammler  1 , Rajendra S Ghadwal  1
Affiliations

Crystalline Divinyldiarsenes and Cleavage of the As=As Bond

Mahendra K Sharma et al. Chemistry. .

Abstract

The first divinyldiarsenes [{(NHC)C(Ph)}As]2 (NHC=IPr 3 a, SIPr 3 b; IPr=C{(NAr)CH}2 ; SIPr=C{(NAr)CH2 }2 ; Ar=2,6-iPr2 C6 H3 ) are reported. Compounds 3 a and 3 b were prepared by the reduction of corresponding chlorides {(NHC)C(Ph)}AsCl2 (NHC=IPr 2 a, SIPr 2 b) with Mg. Calculations revealed a small HOMO-LUMO energy gap of 3.86 (3 a) and 4.24 eV (3 b). Treatment of 3 a with (Me2 S)AuCl led to the cleavage of the As=As bond to restore 2 a, which is expected to proceed via the diarsane [{(IPr)C(Ph)}AsCl]2 (4). Remarkably, 4 as well as 2 a can be selectively accessed on treatment of 3 a with an appropriate amount of C2 Cl6 . Moreover, 3 a readily reacts with PhEEPh (E=Se or Te) at room temperature to give {(IPr)C(Ph)}As(EPh)2 (E=Se 5 a; Te 5 b), revealing the cleavage of As=As and E-E bonds and the formation of As-E bonds. Such highly selective stepwise oxidation (3 a→4→2 a) and bond metathesis (3 a→5 a,b) reactions are unprecedented in main-group chemistry.

Keywords: arsenic; double bond; main-group elements; pi conjugation; vinyl.

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