Diego M. Andrada
Faculty of Natural Sciences and Technology, Department of Chemistry, Saarland University, Campus
Saarbrücken, 66123 Saarbrücken, Saarland, Federal Republic of Germany
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In the last decades, there has been continuous excitement surrounding the discovery of unusual types of bonds, which have led in the recent past to fascinating debates on fundamental questions about the definition of chemical bonding. [1] In particular, the heavier low-valent and unsaturated main group compounds have stirred the interest of scientists by exhibiting a diverse range of captivating and unpredictable chemistry, including some unique bond-activating reactions. [2] The use of large, sterically crowded substituents to kinetically and thermodynamically stabilize otherwise reactive motifs represented a landmark achievement. [3] In addition to that, the concept of using strong Lewis bases to stabilize low-valent main group species through the donor-acceptor interaction arose. The idea of using σ-donor ligands (L) like N-heterocyclic carbenes (NHC) turned out to be the key to broaden the scope in this area by blocking reactive sides with a non-oxidative coordination. [4] These concepts prompted the experimental achievement of compounds containing zero-valent atoms (EL 2 ) double and triple bonds (E 2 L 2 ) and cyclic fragments aromatic and non-aromatic (E 3 L 3 ) between elements of the Groups 13, 14 and 15 (Scheme).
Scheme. Low-valent main group compounds scaffolds. E: main group element; L; Lewis base.
The rational design of novel compounds for their synthesis and application in catalysis and inorganic materials as pre-established scaffolds requires a deep understanding of the connection between electronic structure properties and activity. This talk will present our efforts to understand the chemical bonding in order to provide chemical descriptors for addressing different inorganic synthesis.
[1] R. C. Fischer, P. P. Power, Chem. Rev. 2010, 110, 3877-3923.
[2] G. Frenking, M. Hermann, D. M. Andrada, N. Holzmann, Chem. Soc. Rev. 2016, 45, 1129-1144.
[3] D. J. Liptrot, P. P. Power, Nat. Rev. Chem. 2017, 1, 1.
[4] V. Nesterov, D. Reiter, P. Bag, P. Frisch, R. Holzner, A. Porzelt, S. Inoue, Chem. Rev. 2018,118, 9678-9842.
Virtual Winter School on Computational Chemistry