Stable Borocyclic Radicals via Frustrated Lewis Pair Hydrogenations

详细信息    查看全文

• 作者：Lauren E. Longobardi ; Lei Liu ; Stefan Grimme ; Douglas W. Stephan
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：March 2, 2016
• 年：2016
• 卷：138
• 期：8
• 页码：2500-2503
• 全文大小：355K
• ISSN：1520-5126

文摘

The synthesis and isolation of stable main group radicals remains an ongoing challenge. Here we report the application of frustrated Lewis pair chemistry to the synthesis of boron-containing radicals. H₂ activation with polyaromatic diones and B(C₆F₅)₃ leads to radical formation in good yields. These radicals are robust; they do not decompose on silica gel or react with O₂ and are stable at 35 °C under N₂ indefinitely. The mechanism of formation is explored experimentally, with support from DFT calculations. EPR and UV/vis spectroscopy as well as cyclic voltammetry data are provided, and the radicals are shown to react with cobaltocenes in one-electron chemical reductions to their corresponding borate anions.