Crystalline Divinyldiarsene Radical Cations and Dications

被引：32

作者：

Sharma, Mahendra K. ^{[1
]}

Blomeyer, Sebastian ^{[1
]}

Neumann, Beate ^{[1
]}

Stammler, Hans-Georg ^{[1
]}

van Gastel, Maurice ^{[2
]}

Hinz, Alexander ^{[3
]}

Ghadwal, Rajendra S. ^{[1
]}

机构：

[1] Univ Bielefeld, Anorgan Mol Chem & Katalyse, Lehrstuhl Anorgan Chem & Strukturchem, Ctr Mol Mat,Fak Chem, Univ Str 25, D-33615 Bielefeld, Germany

[2] Max Planck Inst Kohlenforsch Mol Theory & Spect, Kaiser Wilhelm Pl 1, D-45470 Mulheim, Germany

[3] Karlsruhe Inst Technol, Inst Inorgan Chem, Engesserstr 15, D-76131 Karlsruhe, Germany

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2019年 / 58卷 / 49期

关键词：

arsenic; dications; main-group compounds; pi ligands; radicals; MAIN-GROUP ELEMENTS; ONE-ELECTRON REDUCTION; CARBENE; PERSISTENT; ANION; IONS;

D O I：

10.1002/anie.201909144

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

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.

引用

页码：17599 / 17603

页数：5

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