Structure and reactivity of radical ions: new twists on old concepts.
Electron transfer is the simplest reaction possible, yet it has a profound impact on the structure and reactivity of organic compounds. These changes allow a new look at some of the fundamental concepts that are used to explain organic chemistry, such as symmetry, aromaticity, and bonding. The results from high-level electronic structure calculations are used to analyze the mechanistic differences in the pericyclic reactions of simple hydrocarbons and their radical cation counterparts. The importance of state symmetry correlation, Jahn-Teller distortions, delocalization, and fractional bonding for the reaction pathways of hydrocarbon radical cations is discussed.
Donoghue
Patrick J
PJ
Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556-5670, USA.
Wiest
Olaf
O
D002412:Cations / Q000737:chemistry; D002625:Chemistry, Organic / Q000379:methods; D003500:Cyclization; D005609:Free Radicals / Q000737:chemistry; D006838:Hydrocarbons / Q000737:chemistry*; D006844:Hydrocarbons, Cyclic / Q000737:chemistry*; D008958:Models, Molecular; D013329:Structure-Activity Relationship; D013816:Thermodynamics
D002412:Cations; D005609:Free Radicals; D006838:Hydrocarbons; D006844:Hydrocarbons, Cyclic