The rate constants for most of the organic radical reactions in solution have been calibrated using indirect kinetic methods with a basis reaction involving hydrogen-atom transfer.  The archetypal fast radical trapping reaction is H-atom transfer from thiophenol, a reaction initially calibrated by Franz and co-workers at the Pacific Northwest Laboratory in 1989.  Subsequent studies in our group extended the fast radical trapping agents to include H-atom transfer from benzeneselenol.  The presentation will highlight the development of fast indirect radical techniques and the methods used for establishing accuracy of the kinetic values.

Calibrating the top end of the radical kinetic scale

243rd National Meeting (2012)

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