Arene-thioether mixed complex radical cations [report]

D.W. Werst
1994 unpublished
Studies of radiolytically generated radical cations in aromatic hydrocarbon solvents have led to the first direct characterizationof monomericthioether radical cations in liquid solution. Observation of these very reactive chemical intermediates is made possible by the great sensitivity of fluorescence-detected magnetic resonance (FDMR) and by solvent stabilization of the thioether radical cations via electron donation. Monomeric thioether radical cationsin arene solvents such as toluene exist
more » ... h as toluene exist as arene-thioether mixed complex radical cationsR the first _-lone pair mixed complex radical cations ever observed. Such orbital interactionsare of fundamental importance for open-shell intermediates as they have consequences for both electronicstructure and reactivity. Thioether radical cations provide a valuable test system to probe the chemical influence of orbital interactionsthat are generic to all _-type and heteroatom-containingorganicradical cations, and magnetic resonance provides unsurpassed structural resolution for condensed-phase paramagnetic intermediates. This research was carried out by D. W. Werst of the Radiation and Photochemistry Group at ANL. Support was providedby the DOE Divisionof Chemical Sciences.
doi:10.2172/10132711 fatcat:izyugsdlvvbtvfsqzytz2m4jkq