Suppr超能文献

光致和热单电子转移:从受阻路易斯酸碱对生成自由基

Photoinduced and Thermal Single-Electron Transfer to Generate Radicals from Frustrated Lewis Pairs.

作者信息

Holtrop Flip, Jupp Andrew R, van Leest Nicolaas P, Paradiz Dominguez Maximilian, Williams René M, Brouwer Albert M, de Bruin Bas, Ehlers Andreas W, Slootweg J Chris

机构信息

Van't Hoff Institute for Molecular Sciences, University of Amsterdam, PO Box 94157, 1090 GD, Amsterdam, The Netherlands.

Department of Chemistry, Science Faculty, University of Johannesburg, PO Box 254, Auckland Park, Johannesburg, South Africa.

出版信息

Chemistry. 2020 Jul 22;26(41):9005-9011. doi: 10.1002/chem.202001494. Epub 2020 Jul 1.

Abstract

Archetypal phosphine/borane frustrated Lewis pairs (FLPs) are famed for their ability to activate small molecules. The mechanism is generally believed to involve two-electron processes. However, the detection of radical intermediates indicates that single-electron transfer (SET) generating frustrated radical pairs could also play an important role. These highly reactive radical species typically have significantly higher energy than the FLP, which prompted this investigation into their formation. Herein, we provide evidence that the classical phosphine/borane combinations PMes /B(C F ) and PtBu /B(C F ) both form an electron donor-acceptor (charge-transfer) complex that undergoes visible-light-induced SET to form the corresponding highly reactive radical-ion pairs. Subsequently, we show that by tuning the properties of the Lewis acid/base pair, the energy required for SET can be reduced to become thermally accessible.

摘要

典型的膦/硼烷受阻路易斯酸碱对(FLPs)以其活化小分子的能力而闻名。一般认为其机制涉及双电子过程。然而,自由基中间体的检测表明,生成受阻自由基对的单电子转移(SET)也可能起重要作用。这些高反应性的自由基物种通常具有比FLP高得多的能量,这促使了对其形成的研究。在此,我们提供证据表明,经典的膦/硼烷组合PMes /B(CF) 和PtBu /B(CF) 都形成了电子供体-受体(电荷转移)复合物,该复合物经可见光诱导的SET形成相应的高反应性自由基离子对。随后,我们表明,通过调节路易斯酸/碱对的性质,SET所需的能量可以降低到热可及的程度。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cc69/7496419/9885266b2009/CHEM-26-9005-g007.jpg

文献检索

告别复杂PubMed语法,用中文像聊天一样搜索,搜遍4000万医学文献。AI智能推荐,让科研检索更轻松。

立即免费搜索

文件翻译

保留排版,准确专业,支持PDF/Word/PPT等文件格式,支持 12+语言互译。

免费翻译文档

深度研究

AI帮你快速写综述,25分钟生成高质量综述,智能提取关键信息,辅助科研写作。

立即免费体验