title: Electron localization and radiation chemistry of amides.
abstract: Alkylamides (such as N,N'-dimethylformamide, N,N'-diethylformamide, and N,N'-dimethylacetamide) are aprotic solvents that are widely used in organic synthesis. These polar molecules have no electron affinity, and it is believed that irradiated liquid and solid amides stabilize excess electrons as cavity-type species analogous to hydrated and ammoniated electrons. In this study, we use isotope substitution and EPR spectroscopy to demonstrate that, in frozen amides, the suspected "cavity electron" is, in fact, a solvent-stabilized monomer anion. Our observations call into question other attributions of such features in the literature, both in low temperature solids and room temperature liquids. We also provide a general scheme describing amide radiolysis, as the related amides are used as metal ion extracting agents in nuclear separations.
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439, USA. shkrob@anl.gov
authors.forename: Ilya A
authors.initials: IA
authors.lastname: Shkrob
authors.forename: Timothy W
authors.initials: TW
authors.lastname: Marin