Separation of the primary and secondary kinetic isotope effects at a reactive center using starting material reactivities. Application to the FeCl3-Catalyzed oxidation of CH bonds with tert-butyl hydroperoxide
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A method is reported for the determination of both the primary and secondary kinetic isotope effects at a reactive center based on starting material reactivities. This allows the determination of the separate KIEs in reactions for which neither product analysis nor absolute rate measurements are applicable. The methodology is applied to the FeCl3-catalyzed oxidation of ethylbenzene with tert-butyl hydroperoxide, which exhibits both a primary isotope effect and a substantial secondary isotope effect.
author list (cited authors)
Merrigan, S. R., Le Gloahec, V. N., Smith, J. A., Barton, D., & Singleton, D. A.