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Rapid Dihydrogen Cleavage by Persistent Nitroxide Radicals under Frustrated Lewis Pair Conditions

机译:沮丧的路易斯对条件下持久性一氧化氮自由基对二氢的快速裂解

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摘要

Persistent radicals undergo hydrogen atom abstraction reactions with a great variety of substrates, but not with dihydrogen. It has now been found that the TEMPO radical splits dihydrogen under mild conditions in the presence of the strong bulky B(C6F5)(3) boron Lewis acid. The reaction is thought to proceed by a typical frustrated Lewis pair mechanism with the TEMPO radical acting as the active Lewis base. The reaction was analyzed by DFT, which indicates that no significant spin density on the hydrogen atoms is accumulated along the H-2 splitting reaction path.
机译:持久性自由基会与多种底物发生氢原子夺取反应,但不会与二氢发生反应。现已发现,在强烈的大体积B(C6F5)(3)硼路易斯酸存在下,TEMPO自由基可在温和条件下裂解二氢。该反应被认为是通过典型的沮丧的路易斯对机理进行的,其中TEMPO自由基充当活性路易斯碱。通过DFT分析该反应,这表明沿H-2分裂反应路径没有在氢原子上积累明显的自旋密度。

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