Schorpp Marcel, Yadav Ravi, Roth Daniel, Greb Lutz
Anorganisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.
Department of Chemistry and Biochemistry-Inorganic Chemistry, Freie Universität Berlin, Fabeckstr. 34/36, 14195, Berlin, Germany.
Angew Chem Int Ed Engl. 2022 Sep 26;61(39):e202207963. doi: 10.1002/anie.202207963. Epub 2022 Aug 25.
Lewis superacids enable the activation of highly inert substrates. However, the permanent presence of a Lewis superacidic center comes along with a constantly increased intolerance toward functional groups or ambient conditions. Herein, we describe a strategy to unleash Lewis superacidity by electromerism. Experimental and computational results indicate that coordinating a Lewis base to Δ-calix[4]pyrrolato-antimony(III) triggers a ligand redox-noninnocent coupled transfer into antimony(V)-state that exhibits Lewis superacidic features. Lewis acidity by electromerism establishes a concept of potential generality for powerful yet robust reagents and on-site substrate activation approaches.
路易斯超强酸能够实现对高度惰性底物的活化。然而，路易斯超强酸性中心的永久存在伴随着对官能团或环境条件的耐受性不断增加。在此，我们描述了一种通过电子异构现象释放路易斯超强酸性的策略。实验和计算结果表明，将路易斯碱与Δ-杯[4]吡咯锑（III）配位会引发配体氧化还原非无辜耦合转移至具有路易斯超强酸性特征的锑（V）态。通过电子异构现象产生的路易斯酸性为强大而稳健的试剂和原位底物活化方法建立了一个具有潜在普遍性的概念。
