Publication - Journal Article Rational design of an argon-binding superelectrophilic anion

Proceedings of the National Academy of Sciences, vol. 116, iss. 17, pp. 8167-8172, 2019

Martin Mayer, Valentin van Lessen, Markus Rohdenburg, Gao-Lei Hou, Zheng Yang, Rüdiger M. Exner, Edoardo Aprà, Vladimir A. Azov, Simon Grabowsky, Sotiris S. Xantheas, Knut R. Asmis, Xue-Bin Wang, Carsten Jenne, Jonas Warneke

Significance Strong electrophilicity usually goes hand in hand with positive charge. In contrast, most negative ions behave like nucleophiles. Here we challenge this conventional wisdom by introducing an apparently counterintuitive idea that anions can, under well-defined circumstances, behave as superelectrophiles and even show superior binding strength and kinetic product stabilization in comparison with typical superelectrophilic cations. Emanating from the most stable gas-phase dianion [B 12 (CN) 12 ] 2− , synthesized here, we generate its superelectrophilic fragment anion [B 12 (CN) 11 ] − , which binds Ar covalently at room temperature. This opens up additional directions for activation of inert compounds and elements.