title: Heterolytic cleavage of a beta-phosphatoxyalkyl radical resulting in phosphate migration or radical cation formation as a function of solvent polarity.
abstract: [formula: see text] The 2-(diethylphosphatoxy)-2-(p-methoxyphenyl)-1,1-dimethylethyl radical (1) reacted to give the benzylic radical product from phosphate migration or a radical cation (or a mixture of the two) as a function of solvent. Smooth acceleration in rates of reactions of 1 in solvents of increasing polarity and consistent entropies of activation indicate that radical 1 reacts by common mechanism irrespective of the final products formed, specifically by initial heterolysis to a radical cation-phosphate anion pair.
authors.affiliation: Department of Chemistry, Wayne State University, Detroit, Michigan 48202, USA.
authors.forename: P O
authors.initials: PO
authors.lastname: Whitted
authors.forename: J H
authors.initials: JH
authors.lastname: Horner
authors.forename: M
authors.initials: M
authors.lastname: Newcomb
authors.forename: X
authors.initials: X
authors.lastname: Huang
authors.forename: D
authors.initials: D
authors.lastname: Crich
mesh_terms: D002412:Cations; D055598:Chemical Phenomena; D002627:Chemistry, Physical; D005609:Free Radicals / Q000737:chemistry*; D007700:Kinetics; D010755:Organophosphates / Q000737:chemistry*; D010782:Photolysis; D012997:Solvents / Q000737:chemistry; D013056:Spectrophotometry, Ultraviolet
chemical_list: D002412:Cations; D005609:Free Radicals; D010755:Organophosphates; D012997:Solvents