Single‐Electron Transfer Reactions in Frustrated and Conventional Silylium Ion/Phosphane Lewis Pairs,Angewandte Chemie International Edition

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Single‐Electron Transfer Reactions in Frustrated and Conventional Silylium Ion/Phosphane Lewis Pairs
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2018-10-18 , DOI: 10.1002/anie.201808922
Anastasia Merk ₁ , Henning Großekappenberg ₁ , Marc Schmidtmann ₁ , Marcel‐Philip Luecke ₂ , Christian Lorent ₂ , Matthias Driess ₂ , Martin Oestreich ₂ , Hendrik F. T. Klare ₂ , Thomas Müller ₁

Affiliation

Silylium ions undergo a single‐electron reduction with phosphanes, leading to transient silyl radicals and the corresponding stable phosphoniumyl radical cations. As supported by DFT calculations, phosphanes with electron‐rich 2,6‐disubstituted aryl groups are sufficiently strong reductants to facilitate this single‐electron transfer (SET). Frustration as found in kinetically stabilized triarylsilylium ion/phosphane Lewis pairs is not essential, and silylphosphonium ions, which are generated by conventional Lewis adduct formation of solvent‐stabilized trialkylsilylium ions and phosphanes, engage in the same radical mechanism. The trityl cation, a Lewis acid with a higher electron affinity, even oxidizes trialkylphosphanes, such as tBu₃P, which does not react with either B(C₆F₅)₃ or silylium ions.

中文翻译：

沮丧的和常规的硅离子/磷路易斯对中的单电子转移反应

硅离子会与膦发生单电子还原，从而产生瞬态甲硅烷基和相应的稳定的膦基自由基阳离子。正如DFT计算所支持的那样，具有富电子2,6-二取代芳基的膦是足够强的还原剂，可促进这种单电子转移（SET）。在动力学上稳定的三芳基甲硅烷基离子/膦路易斯对中发现的挫败不是必需的，并且由溶剂稳定的三烷基甲硅烷基离子和膦的常规路易斯加合物形成产生的甲硅烷基phosph离子具有相同的自由基机理。三苯甲基阳离子（一种具有较高电子亲和力的路易斯酸）甚至会氧化三烷基膦，例如t Bu ₃ P，而后者不会与任何B（C₆ F ₅）₃或甲硅烷基离子。

更新日期：2018-10-18

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