Reactivity, Structure, and Bonding of Main-Group Compounds: Insights from Theory

Shailja Jain
Institute for Theoretical Chemistry, University of Stuttgart, Stuttgart, Allemagne

Mercredi 15 Janvier 2025, 11H00
Bibiothèque du LCT, Couloir 12-13, 4^ème étage, Campus Pierre et Marie Curie

Here, we explore two advancements in main-group chemistry: (i) the reactivity and (ii) the structure and bonding of main-group compounds. The first study investigates the activation of dinitrogen (N₂), an abundant but inert molecule with a strong triple bond. To utilize N₂ for conversion into useful compounds like fertilizers, one must break its strong triple bond. We investigated the potential of frustrated Lewis pairs (FLPs) for N₂ activation. We demonstrate that oriented external electric fields (OEEFs) facilitate FLP-mediated N₂ activation, highlighting the synergistic potential of FLPs and OEEFs.
The second study explores the aromaticity and π-delocalization of the pentazolate anion ([cyclo-N₅]^-) and its iso-π-electronic systems ([cyclo-P₅]^- and [cyclo-(CH)₅]^-). Pentazolate, a high-energy density material possibly decomposing into N₂ and N₃^-, prompted curiosity about how such highly reactive materials can be stabilized. Through valence-bond and aromaticity analyses, we reveal significant resonance stabilization and robust π-aromaticity, shedding light on the factors that contribute to the stability of this compound.
These studies deepen our understanding of reactivity and bonding in main-group compounds and may assist experimentalists in developing metal-free N2 reduction and new molecules.