ChemInform Abstract: Transition State Structure Variation in the Diels-Alder Reaction from Secondary Deuterium Kinetic Isotope Effects: The Reaction of a Nearly Symmetrical Diene and Dienophile Is Nearly Synchronous.

ChemInform ◽  
1987 ◽  
Vol 18 (50) ◽  
Author(s):  
J. J. GAJEWSKI ◽  
K. B. PETERSON ◽  
J. R. KAGEL
Keyword(s):  
Transition State ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Alder Reaction ◽  
Diels Alder ◽  
State Structure ◽  
Transition State Structure ◽  
Structure Variation ◽  
Kinetic Isotope ◽  
Diels Alder Reaction

Secondary Kinetic Isotope Effects in Bimolecular Nucleophilic Substitutions. V. The Role of the Solvent in the Reaction Between Methyl Iodide and Pyridine

1972 ◽  
Vol 50 (7) ◽  
pp. 982-985 ◽  
Author(s):  
K. T. Leffek ◽  
A. F. Matheson
Keyword(s):  
Transition State ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
State Structure ◽  
Transition State Structure ◽  
Initial State ◽  
Nucleophilic Substitutions ◽  
Kinetic Isotope ◽  
Deuterium Isotope Effects

Secondary kinetic deuterium isotope effects are presented for the reaction of methyl-d3 iodide and pyridine in four different solvents. Calculations on mass and moment of inertia change with deuteration in the initial state and an assumed tetrahedral transition state, together with internal rotational effects, are used to rationalize the inverse isotope effects. It is concluded from the variation of the isotopic rate ratio, that the transition state structure varies with solvent.

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