Reactions in Nitroimidazole Triggered by Low-Energy (0-2 eV) Electrons: Methylation at N1-H Completely Blocks Reactivity

Low‐energy electrons (LEEs) at energies of less than 2 eV effectively decompose 4‐nitroimidazole (4NI) by dissociative electron attachment (DEA). The reactions include simple bond cleavages but also complex reactions involving multiple bond cleavages and formation of new molecules. Both simple and c...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2014-11, Vol.53 (45), p.12240-12243
Main Authors: Tanzer, Katrin, Feketeová, Linda, Puschnigg, Benjamin, Scheier, Paul, Illenberger, Eugen, Denifl, Stephan
Format: Article
Language:English
Subjects:
Atomic and Molecular Clusters
Bonding
Channels
Cleavage
Communications
Decomposition
Electron attachment
Energy of dissociation
Formations
gas-phase reactions
Low energy
low-energy electrons
mass spectrometry
metastable compounds
Methylation
Nitroimidazoles - chemistry
Physics
reaction mechanisms
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Summary:Low‐energy electrons (LEEs) at energies of less than 2 eV effectively decompose 4‐nitroimidazole (4NI) by dissociative electron attachment (DEA). The reactions include simple bond cleavages but also complex reactions involving multiple bond cleavages and formation of new molecules. Both simple and complex reactions are associated with pronounced sharp features in the anionic yields, which are interpreted as vibrational Feshbach resonances acting as effective doorways for DEA. The remarkably rich chemistry of 4NI is completely blocked in 1‐methyl‐4‐nitroimidazole (Me4NI), that is, upon methylation of 4NI at the N1 site. These remarkable results have also implications for the development of nitroimidazole based radiosensitizers in tumor radiation therapy. Low‐energy electrons (LEEs) with energies of less than 2 eV effectively decompose the 4‐nitroimidazole molecule by electron attachment. Thereby a variety of decomposition channels are observed involving simple bond cleavages but also complex reactions involving multiple bond cleavages and formation of new molecules. This rich chemistry induced by LEE is completely suppressed in the energy domain below 2 eV for the molecule in its methylated form.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201407452