Direct Detection of Ion Pair Formation and Collapse in a Migration Reaction of a β-Phosphate Radical

Organic Letters

Volumn 5, Issue 26, 2003, Pages 5055-5058

  Bagnol, Laurent ^a   Horner, John H ^a   Newcomb, Martin ^a  

^a UNIVERSITY OF ILLINOIS AT CHICAGO   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BETA PHOSPHATE; PHOSPHATE; RADICAL; TOLUENE DERIVATIVE; TRIFLUOROETHANOL; TRIFLUOROTOLUENE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL REACTION; ENTROPY; FRAGMENTATION REACTION; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0347916936     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol036052l     Document Type: Article

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24. Unusual solvent character of the mixtures of TFE in aromatic solvents found in this work also deserves note. The mixtures act as highly polar solvents for ion-forming reactions but as low-polarity solvents for ion pair escape processes. This behavior permitted direct detection of ion pairs with exceptionally long lifetimes, a property that can be exploited in studies of many ion pair reactions. We note that 5% of the polar solvent TFE in toluene and in TFT appeared to result in a constant offset of the polarity of the parent solvents (see Figure 3), suggesting that mixtures of TFE in solvents less polar than toluene might increase the operating polarity range of these exotic mixtures and provide media in which ion pairs have even longer lifetimes than those found here.