An ene reaction with a polar transition state as ascertained from solvent effects

1991 ◽  
Vol 4 (10) ◽  
pp. 605-610 ◽  
Author(s):  
Pierre Laszlo ◽  
Michelle Teston-Henry
Keyword(s):  
Transition State ◽  
Solvent Effects ◽  
Ene Reaction ◽  
Polar Transition

On the Calculation of Transition State Activity Coefficient and Solvent Effects on Chemical Reactions

1998 ◽  
Vol 63 (12) ◽  
pp. 1969-1976 ◽  
Author(s):  
Alvaro Domínguez ◽  
Rafael Jimenez ◽  
Pilar López-Cornejo ◽  
Pilar Pérez ◽  
Francisco Sánchez
Keyword(s):  
Activity Coefficient ◽  
Transition State ◽  
Chemical Reactions ◽  
Solvent Effects ◽  
Transition State Theory ◽  
Reaction Medium ◽  
State Theory ◽  
Precursor Complex ◽  
State Activity ◽  
Classical Transition

Solvent effects, when the classical transition state theory (TST) holds, can be interpreted following the Brønsted equation. However, when calculating the activity coefficient of the transition state, γ# it is important to take into account that this coefficient is different from that of the precursor complex, γPC. The activity coefficient of the latter is, in fact, that calculated in classical treatments of salt and solvent effects. In this paper it is shown how the quotients γ#/γPC change when the reaction medium changes. Therefore, the conclusions taken on the basis of classical treatments may be erroneous.

THE ALKALINE CLEAVAGE OF o-NITROBENZYLTRIMETHYLSILANE SOLVENT EFFECTS IN THE DIOXANE–WATER SYSTEM

1963 ◽  
Vol 41 (6) ◽  
pp. 1525-1530 ◽  
Author(s):  
H. R. Allcock
Keyword(s):  
Transition State ◽  
Solvent Effects ◽  
Water System ◽  
Solvent Polarity ◽  
High Water ◽  
Aqueous Dioxane ◽  
Alkaline Cleavage ◽  
Rate Of Reaction ◽  
Kinetics Of

The kinetics of alkaline cleavage of o-nitrobenzyltrimethylsilane were examined in aqueous dioxane media. At high water concentrations, increases in solvent polarity retard the cleavage, as required by a mechanism involving charge dispersion in the transition state. At high dioxane concentrations, solvent polarity increases are accompanied by increases in the rate of reaction, a result which may reflect association between the solvent components.

Initial state and transition state contributions to solvent effects on activation enthalpies for substitution reactions of tris(1,10-phenanthroline)iron(II) in aqueous methanol

1983 ◽  
Vol 8 (3) ◽  
pp. 148-152 ◽  
Author(s):  
Michael J. Blandamer ◽  
John Burgess ◽  
Timothy Digman ◽  
Philip P. Duce ◽  
John P. McCann ◽  
...  
Keyword(s):  
Transition State ◽  
Solvent Effects ◽  
Aqueous Methanol ◽  
Substitution Reactions ◽  
Initial State
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