Independent LUMO Reactivity in Mesoionic N-Heterocyclic Thiones: Synthesis of a Stable Radical Anion
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Updated: Jun 10, 2025

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization
Published on: November 29, 2018
Subir Maji1, Biplab Gope1, Madhur Sharma2
1Department of Chemical Sciences, Indian Institute of Science Education and Research Kolkata, Mohanpur, 741246, India.
Abstract:
Mesoionic compounds, with positive and negative charges, are expected to have dual-site highest occupied molecular orbital (HOMO, donor) and lowest unoccupied molecular orbital (LUMO, acceptor) reactivity. Herein, we report a novel class of air-stable mesoionic N-heterocyclic thiones (mNHTs) synthesized from abnormal N-heterocyclic carbenes (aNHCs). DFT studies revealed a highly polarized exocyclic thione moiety and computed Fukui function analysis suggests the dual-site HOMO/LUMO reactivity of mNHTs predicting donor property at the negatively charged 'S' center while acceptor property at the cationic imidazole ring. The independent LUMO reactivity of the mNHT was realized by its chemical reduction to an elusive radical anion, which was characterized by a single crystal X-raydiffraction study. Further, we explore the reactivity of radical anion for the activation of SO2 gas, C-Br bonds of aryl bromide and photocatalytic functionalization of C-X (X = F, Br) bonds. This work unlocks the independent LUMO reactivity of a mesoionic compound.
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