The chemical bond is a fundamental concept in every aspect of chemistry. Controlling and fine-tuning the strength, reactivity, and stability have a direct technological impact. Although compounds featuring hydrogen, carbon, and nitrogen atoms bring well- established bonding motifs, the scope for heavier analogues is narrower. For instance, multiple bonds between heavy main group elements had been remained unrealized. Thus, the so-called “double-bond rule” emerged, formalizing the impossibility of achieving them due to the relative weakness of π-bonds. Eventually, synthetic strategies, based on sterically crowded substituents to provide kinetic and thermodynamic stability, brought homodiatomic examples like Sn=Sn, disproving this rule.[1] Their isoelectronic heterodiatomic molecules with a multiple bond group 13 (E13) and group 15 (E15) are preparatively more challenging. The bonding contains a significant ionic component, which makes them prone to oligomerization. Endeavours to control the reactivity and stability of these multiple bonds are driven by their promising applications as functional single-source precursors for III−V semiconductor materials, hydrogen storage, and fixation of greenhouse gases.

This presentation showcases the synergy between experimental and computational chemistry tools to foresee and gain synthetic access exotic boding motifs on group 13 and group 15 compounds.[2,3] The approach rests not only on the stabilization provided by the volume of flaking groups but also on the electronic features enforced by strong σ-donor Lewis bases.[4] Besides, depending on the nature of the E13 (B or Al), E15 (N and P), and side groups, the reactivity can be customized to specific needs.[5]

References
[1] R. C. Fischer, P. P. Power, Chem. Rev. 2010, 110, 3877.
[2] A. Koner, T. Sergeieva, B. Morgenstern, D. M. Andrada, Inorg. Chem. 2021, 60, 14202.
[3] A. Koner, B. Morgenstern, D. M. Andrada, Angew. Chem. Int. Ed. 2022, 61, e202203345.
[4] G. Frenking, M. Hermann, D. M. Andrada, N. Holzmann, Chem. Soc. Rev. 2016, 45, 1129.
[5] D. Mandal, T.I. Demirer, T. Sergeieva, B. Morgenstern, H.T.A. Wiedemann, C.W.M. Kay, D.M. Andrada Angew. Chem. Int. Ed. 2022 (under revision).