Nazish Mohd, Legendre Christina M, Sarkar Samir Kumar, Lücken Jana, Goffitzer Daniel J, Diefenbach Martin, Schwederski Brigitte, Herbst-Irmer Regine, Stalke Dietmar, Holthausen Max C, Kaim Wolfgang, Roesky Herbert W
Institut für Anorganische Chemie, Universität Göttingen, Tammannstrasse 4, Göttingen 37077, Germany.
Institut für Anorganische und Analytische Chemie, Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, Frankfurt am Main 60438, Germany.
Inorg Chem. 2021 Jul 19;60(14):10100-10104. doi: 10.1021/acs.inorgchem.1c01438. Epub 2021 Jul 2.
Herein, we report on a facile and selective one-pot synthetic route to silicon-boron radicals. Reduction of BrBTip (Tip = 2,4,6-PrCH) with KC in the presence of LSi-R affords LSi(Bu)-B(Br)Tip () and LSi(N(TMS))-B(Br)Tip () [L = PhC(NBu)]. These first examples of silicon-boron isolated radical species feature spin density on the silicon and boron atoms. and exhibit extraordinary stability to high temperatures under inert conditions in solution and air stability in the solid state. Both radicals have been isolated and fully characterized by electron paramagnetic resonance spectroscopy, SQUID magnetometry, mass spectrometry, cyclic voltammetry, single-crystal X-ray structure analysis, and density functional theory calculations. Moreover, compound exhibits one-electron transfer when treated with 1 equiv of AgSOCF and [PhC][B(CF)], respectively, resulting in the corresponding cations [LSi(Bu)-B(Br)Tip][CFSO] () and [LSi(Bu)-B(Br)Tip][B(CF)] (). Compounds and have been characterized with multinuclear NMR and mass spectrometry.
在此，我们报道了一种简便且选择性的一锅法合成硅硼自由基的路线。在LSi-R存在下，用KC还原BrBTip（Tip = 2,4,6-PrCH）得到LSi(Bu)-B(Br)Tip（）和LSi(N(TMS))-B(Br)Tip（）[L = PhC(NBu)]。这些首次报道的孤立硅硼自由基物种在硅和硼原子上具有自旋密度。 和 在惰性条件下的溶液中对高温表现出非凡的稳定性，在固态下具有空气稳定性。这两种自由基均已通过电子顺磁共振光谱、超导量子干涉仪磁力测定法、质谱、循环伏安法、单晶X射线结构分析和密度泛函理论计算进行了分离和全面表征。此外，化合物 在用1当量的AgSOCF和[PhC][B(CF)]分别处理时表现出单电子转移，生成相应的阳离子[LSi(Bu)-B(Br)Tip][CFSO]（）和[LSi(Bu)-B(Br)Tip][B(CF)]（）。化合物 和 已通过多核NMR和质谱进行了表征。
