Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig, 04103 Leipzig, Germany.
Anorganische Chemie, Fakultät für Mathematik und Naturwissenschaften, Bergische Universität Wuppertal, 42119 Wuppertal, Germany.
Proc Natl Acad Sci U S A. 2019 Apr 23;116(17):8167-8172. doi: 10.1073/pnas.1820812116. Epub 2019 Apr 5.
Chemically binding to argon (Ar) at room temperature has remained the privilege of the most reactive electrophiles, all of which are cationic (or even dicationic) in nature. Herein, we report a concept for the rational design of anionic superelectrophiles that are composed of a strong electrophilic center firmly embedded in a negatively charged framework of exceptional stability. To validate our concept, we synthesized the percyano-dodecoborate [B(CN)], the electronically most stable dianion ever investigated experimentally. It serves as a precursor for the generation of the monoanion [B(CN)], which indeed spontaneously binds Ar at 298 K. Our mass spectrometric and spectroscopic studies are accompanied by high-level computational investigations including a bonding analysis of the exceptional B-Ar bond. The detection and characterization of this highly reactive, structurally stable anionic superelectrophile starts another chapter in the metal-free activation of particularly inert compounds and elements.
在室温下与氩气（Ar）发生化学结合仍然是最活泼的亲电试剂的特权，所有这些亲电试剂本质上都是阳离子（甚至是二阳离子）。在此，我们报告了一种合理设计阴离子超亲电试剂的概念，该试剂由一个强的亲电中心牢固地嵌入在异常稳定的带负电荷的框架中。为了验证我们的概念，我们合成了全氰十二硼酸盐[B(CN)]，这是实验上研究过的电子最稳定的二阴离子。它可用作生成单价阴离子[B(CN)]的前体，后者确实可以在 298 K 下自发与 Ar 结合。我们的质谱和光谱研究伴随着高水平的计算研究，包括对特殊 B-Ar 键的键合分析。这种高反应性、结构稳定的阴离子超亲电试剂的检测和表征开启了无金属激活特别惰性化合物和元素的新篇章。
