Carbon and secondary deuterium kinetic isotope effects on SN2 methyl transfer reactions

2007 ◽  
Vol 20 (12) ◽  
pp. 1114-1120 ◽  
Author(s):  
Joanna Dzierzawska ◽  
Arkadiusz Jarota ◽  
Michal Karolak ◽  
Lukasz Piotrowski ◽  
Izabela Placek ◽  
...  
Keyword(s):  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Transfer Reactions ◽  
Kinetic Isotope ◽  
Methyl Transfer

Ab initio predictions and experimental confirmation of large tunneling contributions to rate constants and kinetic isotope effects for hydrogen atom transfer reactions

1986 ◽  
Vol 108 (12) ◽  
pp. 3515-3516 ◽  
Author(s):  
Bruce C. Garrett ◽  
Donald G. Truhlar ◽  
Joel M. Bowman ◽  
Albert F. Wagner ◽  
Daniel. Robie ◽  
...  
Keyword(s):  
Hydrogen Atom ◽  
Ab Initio ◽  
Rate Constants ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Hydrogen Atom Transfer ◽  
Experimental Confirmation ◽  
Transfer Reactions ◽  
Atom Transfer ◽  
Kinetic Isotope

scholarly journals Does the pressure dependence of kinetic isotope effects report usefully on dynamics in enzyme H‐transfer reactions?

FEBS Journal ◽  
2015 ◽  
Vol 282 (16) ◽  
pp. 3243-3255 ◽  
Author(s):  
Robin Hoeven ◽  
Derren J. Heyes ◽  
Sam Hay ◽  
Nigel S. Scrutton
Keyword(s):  
Pressure Dependence ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Transfer Reactions ◽  
Kinetic Isotope

Theoretical simulation of Brønsted correlations for proton transfer and methyl transfer: the significance of the Brønsted coefficient β

1999 ◽  
Vol 77 (5-6) ◽  
pp. 830-841 ◽  
Author(s):  
Ian H Williams ◽  
Paul A Austin
Keyword(s):  
Proton Transfer ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Molecular Orbital Calculations ◽  
Theoretical Simulation ◽  
Kinetic Isotope ◽  
Methyl Transfer ◽  
Equilibrium Relationship ◽  
Substituted Pyridines ◽  
Very High

Brønsted correlations for proton transfer and methyl transfer between pairs of mimicked 4-substituted pyridines have been simulated by means of AM1 molecular orbital calculations. The enthalpies of activation and of reaction are well correlated by the Marcus relation. The Brønsted correlation is markedly curved for proton transfer for which the Marcus intrinsic barrier is very low (~ 5 kJ mol-1). Conversely, the Brønsted correlation is almost imperceptibly curved for methyl transfer for which the Marcus intrinsic barrier is very high (~ 152 kJ mol-1). The slope of the Brønsted correlation provides an approximate measure of the position of the transition structure along the reaction coordinate between the reactant and product encounter complexes. Primary kinetic isotope effects for proton transfer show a broad maximum, centered on ΔHrxn = 0, when plotted against reaction exo/endothermicity only if computed with respect to isolated acids and bases, but intracomplex kinetic isotope effects show a maximum displaced significantly towards the endothermic proton transfers.Key words: Brønsted correlation, rate-equilibrium relationship, transition state, isotope effect.

Steric Effects on the Primary Isotope Dependence of Secondary Kinetic Isotope Effects in Hydride Transfer Reactions in Solution: Caused by the Isotopically Different Tunneling Ready State Conformations?

2015 ◽  
Vol 137 (20) ◽  
pp. 6653-6661 ◽  
Author(s):  
Binita Maharjan ◽  
Mahdi Raghibi Boroujeni ◽  
Jonathan Lefton ◽  
Ormacinda R. White ◽  
Mortezaali Razzaghi ◽  
...  
Keyword(s):  
Isotope Effects ◽  
Hydride Transfer ◽  
Kinetic Isotope Effects ◽  
Transfer Reactions ◽  
Steric Effects ◽  
Kinetic Isotope ◽  
Hydride Transfer Reactions
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