SET–driven radical formation in nitroaromatics

Kimika Teorikoa Seminar

Knowledge of radical electronic structures enables the control of their properties and opens the potential of fine controlling their reactivity. Therefore, EPR is an unmatched technique, needed for the electronic structure characterization of organic radicals. However, the reactive nature of radicals and non-trivial preparational requirements limit the number of usable radical species until now. Enabling the generation of radical species under simple reaction conditions, employing available and inexpensive reactants, is therefore the key component for harnessing the extraordinary properties of organic radicals. In our recent work on nitrobenzene, we uncovered a radical formation process by a thermal single electron transfer (SET) from multiple anionic organo-bases.[1] I will show how the scope of this SET-driven radical formation can be expanded to the wider family of nitroaromatics, employing cw-EPR spectroscopy and DFT calculations. The understanding of the electronic structures of these radical pairs enables the utilization of radical compounds as reacting agents under mild synthetic conditions, laying the foundation for a new class of distinctive reaction mechanisms and thus unexplored opportunities in organic synthesis.

[1] Balahoju S., Bhattacharjee N., Lezama L., Lopez X., Salcedo-Abraira P., Rodríguez-Diéguez A., Reta D., Radical Formation by Direct Single Electron Transfer between Nitrobenzene and Anionic Organo Bases, ACS Omega,
2025, 10, 23798-23807