Chemistry Department, Namur Institute of Structured Matter, University of Namur, 61 rue de Bruxelles, 5000, Namur, Belgium.
Chemistry. 2023 Jul 6;29(38):e202301146. doi: 10.1002/chem.202301146. Epub 2023 May 11.
Isolation and characterization of highly reactive intermediates are crucial to understand the nature of chemical reactivity. Accordingly, the reactivity of weakly coordinating anions (WCA), usually used to stabilized cationic super electrophiles are of fundamental interest. When a variety of WCA are known to form stable σ-complexes with a proton, inducing Brønsted super acidity, bis-coordinated weak-coordinated anions are much more elusive and considered as long-sought reactive species. In this work, the chemistry of borylated sulfate, triflimidate and triflate anions were scouted in details with the aim of synthetizing the unique analogs of protonated Brønsted superacids. Those complexes were formed by successive borylation with a 9-boratriptycene derived Lewis super acid paired with a weak coordinated anion, characterized in solution and in the solid state and exhibit unique structures and reactivities.
分离和表征高反应性中间体对于理解化学反应性的本质至关重要。因此，弱配位阴离子（WCA）的反应性，通常用于稳定阳离子超亲电试剂，具有根本的重要性。当各种 WCA 已知与质子形成稳定的σ-配合物，诱导布朗斯台德超酸时，双配位的弱配位阴离子则更加难以捉摸，被认为是长期以来寻求的反应性物质。在这项工作中，详细研究了硼酸化硫酸盐、三氟甲磺酸酯和三氟甲磺酸根阴离子的化学性质，旨在合成质子化布朗斯台德超强酸的独特类似物。这些配合物是通过与衍生自路易斯超强酸的 9-硼三嗪的连续硼化形成的，与弱配位阴离子配对，在溶液中和固态中进行了表征，并表现出独特的结构和反应性。
