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首页> 外文期刊>Chemistry: A European journal >Synergistic Effects of Lewis Bases and Substituents on the Electronic Structure and Reactivity of Boryl Radicals
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Synergistic Effects of Lewis Bases and Substituents on the Electronic Structure and Reactivity of Boryl Radicals

机译：Lewis碱和取代基对硼基自由基电子结构和反应活性的协同作用

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摘要

Boryl radicals have the potential for the development of new molecular entities and for application in new radical reactions. However, the effects of the substituents and coordinating Lewis bases on the reactivity of boryl radicals are not fully understood. By using first-principles methods, we investigated the spin-density distribution and reactivity of a series of boryl radicals with various substituents and Lewis bases. The substituents, along with the Lewis bases, only affect the radical reactivity when an unpaired electron is in the boron p_z orbital, that is, for three-coordinate radicals. We found evidence of synergistic effects between the substituents and the Lewis bases that can substantially broaden the tunability of the reactivity of the boryl radicals. Among Lewis bases, pyridine and imidazol-2-ylidene show a similar capacity for stabilization by delocalizing the spin density. Electron-donating substituents, such as nitrogen, more efficiently stabilize boryl radicals than oxygen and carbon atoms. The reactivity of a boryl radical is always boron based, irrespective of the spin density on boron.
机译：硼自由基具有开发新分子实体和应用于新自由基反应的潜力。但是，对取代基和配位的路易斯碱对硼基自由基反应性的影响尚不完全清楚。通过使用第一性原理方法，我们研究了具有各种取代基和Lewis碱的一系列硼基的自旋密度分布和反应性。当未配对的电子在硼p_z轨道上，即对于三配位基团时，取代基与路易斯碱一起仅影响基团反应性。我们发现了取代基和路易斯碱之间的协同效应的证据，该协同效应可大大拓宽硼基自由基反应性的可调性。在路易斯碱中，吡啶和咪唑-2-亚基通过使自旋密度离域而显示出相似的稳定能力。电子给体取代基（例如氮）比氧和碳原子更有效地稳定硼烷基。硼自由基的反应性始终基于硼，而与硼的自旋密度无关。

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