ORGN 768 |
| The kinetics of intramolecular hydrogen atom transfer reactions were investigated by laser flash photolysis. PTOC ester radical precursors were photolyzed to yield carbon radicals that undergo 1,5- and 1,6-hydrogen atom transfer reactions to give UV-detectable trityl and diphenyl radicals. At 20 °C, hydrogen atom transfers yielding trityl radicals have rate constants of 3.5 × 106 s-1 and 3.1 × 105 s-1 respectively for 1,5 and 1,6 transfers. DFT calculations (B3LYP) predict minor differences in activation energies between the 1,5- and 1,6-abstractions, consistent with experimental results derived from Arrhenius functions.
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Physical Organic Chemistry: Calculations, Mechanisms, Photochemistry, and High Energy Species
8:00 AM-12:00 PM, Thursday, March 29, 2007 McCormick Place Lakeside -- Room E451A/B, Level 4, Oral
Division of Organic Chemistry |
