Separation of the primary and secondary kinetic isotope effects at a reactive center using starting material reactivities. Application to the FeCl3-Catalyzed oxidation of CH bonds with tert-butyl hydroperoxide

1999 ◽  
Vol 40 (20) ◽  
pp. 3847-3850 ◽  
Author(s):  
Steven R. Merrigan ◽  
Valerie N. Le Gloahec ◽  
Jason A. Smith ◽  
Derek H.R. Barton ◽  
Daniel A. Singleton
Keyword(s):  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Starting Material ◽  
Butyl Hydroperoxide ◽  
Tert Butyl ◽  
Kinetic Isotope ◽  
Reactive Center ◽  
Tert Butyl Hydroperoxide ◽  
Catalyzed Oxidation

SOME DEUTERIUM KINETIC ISOTOPE EFFECTS: IV. β-DEUTERIUM EFFECTS IN WATER SOLVOLYSIS OF ETHYL, ISOPROPYL, AND tert-BUTYL COMPOUNDS

1960 ◽  
Vol 38 (11) ◽  
pp. 2171-2177 ◽  
Author(s):  
K. T. Leffek ◽  
J. A. Llewellyn ◽  
R. E. Robertson
Keyword(s):  
Isotope Effect ◽  
Kinetic Isotope Effect ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Alkyl Halides ◽  
Tert Butyl ◽  
Kinetic Isotope ◽  
Deuterium Isotope Effects ◽  
Intramolecular Forces

The secondary β-deuterium isotope effects have been measured in the water solvolytic reaction of alkyl halides and sulphonates for primary, secondary, and tertiary species. In every case the kinetic isotope effect was greater than unity (kH/kD > 1). This isotope effect may be associated with varying degrees of hyperconjugation or altered non-bonding intramolecular forces. The experiments make it difficult to decide which effect is most important.

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