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Volumn 121, Issue 46, 1999, Pages 10685-10694

β-Phosphatoxyalkyl radical reactions: Competing phosphate migration and phosphoric acid elimination from a radical cation-phosphate anion pair formed by heterolytic fragmentation

Author keywords

[No Author keywords available]

Indexed keywords

ANION; CATION; FREE RADICAL; PHOSPHATE; PHOSPHORIC ACID;

EID: 0033601068     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja991012r     Document Type: Article
Times cited : (58)

References (41)
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    • -1 at 20°C. Given the low concentrations of precursor and radicals in the LFP experiments, this dynamic process cannot be due to radical-radical or radical-precursor reactions, and we ascribe it to a unimolecular process. Apparently, radical 3 was initially produced in a nonequilibrium distribution of conformations and relaxed rapidly by bond rotation.
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    • note
    • 14 in THF were similar to those observed in acetonitrile. Quantitative measurements of the ratios of products by the method used for the product ratios in acetonitrile were not possible because the overall reactions were too slow in THF. Depletion of radicals by competitive radical - radical reactions in THF would lead to overestimation of the amounts of radical 2.
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    • An experiment in an aqueous acetonitrile solution reported in our preliminary communication (ref 6) gave the same pseudo-first-order rate constant for growth at 360 nm as found here, but the temporal resolution in that experiment was not adequate for detection of the fast signal growth at 390 nm. The kinetic results in this work for aqueous solutions were obtained with a fast oscilloscope using 0.5 or 1.0 ns resolution.
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    • note
    • An alternative to two-electron processes within the CIP of radical cation 4 and phosphate anion is possible. Electron transfer in the CIP of 4 and diphenyl phosphate anion would give the styrene and a phosphatoxyl radical which will be quite reactive. For example, our computational results indicated that the transition state for H-atom transfer from isobutene to the dimethylphosphatoxyl radical was lower in energy than the weakly bound ensemble.
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    • Following the submission of this work, we found a β-phosphatoxyalkyl radical that reacts by heterolytic cleavage resulting in phosphate migration and/or formation of diffusively free radical cation as a function of solvent polarity. See: Whitted, P. O.; Horner, J. H.; Newcomb, M.; Huang, X.; Crich, D. Org. Lett. 1999, 1, 153-156.
    • (1999) Org. Lett. , vol.1 , pp. 153-156
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