Sharma Mahendra K, Blomeyer Sebastian, Neumann Beate, Stammler Hans-Georg, van Gastel Maurice, Hinz Alexander, Ghadwal Rajendra S
Anorganische Molekülchemie und Katalyse, Lehrstuhl für Anorganische Chemie und Strukturchemie, Centrum für Molekulare Materialien, Fakultät für Chemie, Universität Bielefeld, Universitätsstr. 25, 33615, Bielefeld, Germany.
Max-Planck-Institut für Kohlenforschung, Molecular Theory and Spectroscopy, Kaiser-Wilhelm-Platz 1, Mülheim an der Ruhr, 45470, Germany.
Angew Chem Int Ed Engl. 2019 Dec 2;58(49):17599-17603. doi: 10.1002/anie.201909144. Epub 2019 Oct 23.
The divinyldiarsene radical cations [{(NHC)C(Ph)}As] (GaCl ) (NHC=IPr: C{(NDipp)CH} 3; SIPr: C{(NDipp)CH } 4; Dipp=2,6-iPr C H ) and dications [{(NHC)C(Ph)}As] (GaCl ) (NHC=IPr 5; SIPr 6) are readily accessible as crystalline solids on sequential one-electron oxidation of the corresponding divinyldiarsenes [{(NHC)C(Ph)}As] (NHC=IPr 1; SIPr 2) with GaCl . 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 As (I=3/2) nuclei.
二乙烯基二砷自由基阳离子{(NHC)C(Ph)}As (NHC = IPr: C{(NDipp)CH} 3; SIPr: C{(NDipp)CH } 4; Dipp = 2,6 - iPr C H )和双阳离子{(NHC)C(Ph)}As (NHC = IPr 5; SIPr 6)可通过相应的二乙烯基二砷[{(NHC)C(Ph)}As](NHC = IPr 1; SIPr 2)与GaCl 进行连续单电子氧化，以结晶固体形式轻松获得。化合物3 - 6已通过X射线衍射、循环伏安法、EPR/NMR光谱、UV/vis吸收光谱以及DFT计算进行了表征。从1和2的HOMO（主要是As - As π键）依次去除一个电子会导致As = As键依次伸长，C - As键从1/2→3/4→5/6收缩。3和4的UV/vis光谱在可见光区域均表现出与SOMO相关跃迁相关的强吸收。3和4的EPR光谱由于未成对电子与两个As (I = 3/2)核的耦合，各自显示出一个变宽的七重峰。
