通过环状烷基（氨基）卡宾稳定的瞬态无环锗（I）自由基的分离
Isolation of Transient Acyclic Germanium(I) Radicals Stabilized by Cyclic Alkyl(amino) Carbenes.
作者信息
Siddiqui Mujahuddin M, Sarkar Samir Kumar, Sinhababu Soumen, Ruth Paul Niklas, Herbst-Irmer Regine, Stalke Dietmar, Ghosh Munmun, Fu Mingxing, Zhao Lili, Casanova David, Frenking Gernot, Schwederski Brigitte, Kaim Wolfgang, Roesky Herbert W
机构信息
Institut für Anorganische Chemie , Universität Göttingen , Tammannstrasse 4 , 37077 , Göttingen , Germany.
Institute of Advanced Synthesis , Nanjing Tech University , Nanjing 211816 , China.
出版信息
J Am Chem Soc. 2019 Feb 6;141(5):1908-1912. doi: 10.1021/jacs.8b13434. Epub 2019 Jan 24.
Despite the notable progress in the stabilization of main group radicals by NHCs and cAACs, no germanium radicals have been isolated so far due to synthetic challenges. Stabilization of neutral [:ER] (E = Si, Ge) radicals is an uphill task, as these reactive transient species are highly susceptible to dimerization. Herein, we report the synthesis of acyclic neutral germanium(I) radicals Cy-cAAC:GeN(SiMe)Dip (1) and Me-cAAC:GeN(SiPh)Mes (2) obtained by the reduction of [Ar(SiR)NGeCl] with KC in the presence of cAAC. Compounds 1 and 2 are well characterized by single crystal X-ray structural analysis, cyclic voltammetry, and EPR spectroscopy. Furthermore, the structure and bonding of compounds 1 and 2 have been investigated by theoretical methods.
尽管氮杂环卡宾（NHCs）和环状（烷基）（氨基）卡宾（cAACs）在稳定主族自由基方面取得了显著进展，但由于合成方面的挑战，到目前为止尚未分离出锗自由基。稳定中性[:ER]（E = Si，Ge）自由基是一项艰巨的任务，因为这些反应性瞬态物种极易二聚。在此，我们报告了通过在cAAC存在下用KC还原[Ar(SiR)NGeCl]得到的无环中性锗（I）自由基Cy-cAAC:GeN(SiMe)Dip（1）和Me-cAAC:GeN(SiPh)Mes（2）的合成。化合物1和2通过单晶X射线结构分析、循环伏安法和电子顺磁共振光谱进行了充分表征。此外，还通过理论方法研究了化合物1和2的结构与键合。
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