Cage effect and inverse temperature dependence of the kinetic isotope effect in the c-C6H12/c-C6D12 reaction with OH radicals in fenton and HOONOH2O systems

2011 ◽  
pp. n/a-n/a ◽  
Author(s):  
Elisey S. Rudakov ◽  
Vladimir L. Lobachev ◽  
Larisa K. Volkova
Keyword(s):  
Temperature Dependence ◽  
Isotope Effect ◽  
Kinetic Isotope Effect ◽  
Oh Radicals ◽  
Cage Effect ◽  
Inverse Temperature ◽  
Kinetic Isotope

Quantum Mechanical Tunneling in Homodienyl Sigmatropic [1,5]-Hydrogen Shifts of (Hydroxymethyl)styrylcyclopropanes

1990 ◽  
Vol 43 (6) ◽  
pp. 1071 ◽  
Author(s):  
GG Pegg ◽  
GV Meehan
Keyword(s):  
Low Temperature ◽  
Temperature Dependence ◽  
Isotope Effect ◽  
Kinetic Isotope Effect ◽  
Natural Compounds ◽  
Quantum Mechanical ◽  
Strong Temperature Dependence ◽  
Quantum Mechanical Tunneling ◽  
Hydrogen Migration ◽  
Kinetic Isotope

The strong temperature dependence of the deuterium kinetic isotope effect observed for homodienyl [1,5]-hydrogen migration of [hydroxy (D)methyl] styrylcyclopropanes (1c,d) in hexane solvent is suggestive of a significant tunnelling contribution to the mechanism. While the hydroxy substituent at the migration origin appears to influence the thermolytic behaviour of these molecules, attempts to promote oxy anionic homodienyl rearrangement in the isotopically natural compounds (1a,b) at low temperature were unsuccessful.

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