Acidity and reactivity of group 13 Lewis acids and superacids

Alexey Y. Timoshkin

St. Petersburg State Uiversity, Institute of Chemistry


Lewis superacids are very important for their practical use in catalysis, in particular as active components of Frustrated Lewis Pairs for the activation of small molecules, for the construction of Weakly Coordinated Anions (which allows studying reactive cationic intermediates), and for stabilization of the unstable molecular forms via donor-acceptor interactions. Principles of construction of strong Lewis acids and Lewis superacids of group 13 elements will be considered. Results of extensive computational studies of group 13 Lewis acids and superacids will be presented and discussed [1-4]. Factors, affecting their acidity will be analyzed, and different Lewis acidity scales will be compared. Importance of the partner donor molecule will be emphasized. Structures and stability of donor-acceptor cryptands, formed by perfluorinated group 13 adamantane derivatives and azaadamantane linked together via aromatic spacer of different length, will be discussed. The reactivity of these donor-acceptor cryptands towards heterolytic splitting of molecular hydrogen will be presented and discussed. The most promising systems for the experimental studies will be recommended. This work was supported by the Russian Science Foundation grant 18-13-00196 References: [1]. Davydova E.I., Sevastianova T.N., Timoshkin A.Y., Coord. Chem. Rev. 2015, 297-298, 91-126. [2]. El Hamdi M., Solà M., Poater J., Timoshkin A. Y., J. Comput. Chem. 2016, 37, 1355-1362. [3]. Timoshkin A.Y., Morokuma K., Phys. Chem. Chem. Phys., 2012, 14, 14911-14916. [4]. Mück L. A., Timoshkin A.Y., Frenking G. Inorg. Chem., 2012, 51, 640646.