Kinetics of deprotonation of arylnitromethanes by benzoate ions in acetonitrile solution. Effect of equilibrium and nonequilibrium transition state solvation on intrinsic rate constants of proton transfers

1992 ◽  
Vol 114 (2) ◽  
pp. 631-637 ◽  
Author(s):  
Joseph R. Gandler ◽  
Claude F. Bernasconi
Keyword(s):  
Transition State ◽  
Rate Constants ◽  
Intrinsic Rate ◽  
Acetonitrile Solution ◽  
Proton Transfers ◽  
Kinetics Of

Kinetics of Proton Transfer Reactions of Carbon Acids. II. Reaction of Di-(4-nitrophenyl)methane with Alkoxide Bases

1972 ◽  
Vol 50 (1) ◽  
pp. 24-30 ◽  
Author(s):  
A. Jarczewski ◽  
K. T. Leffek
Keyword(s):  
Proton Transfer ◽  
Transition State ◽  
Rate Constants ◽  
Activation Parameters ◽  
Transfer Reactions ◽  
Activation Process ◽  
Proton Transfers ◽  
Proton Transfer Reactions ◽  
Carbon Acids ◽  
Kinetics Of

The second-order rate constants have been measured over a range of temperatures for the proton-transter reactions from di-(4-nitrophenyl)methane to ethoxide, isopropoxide, and t-butoxide ions in solvents consisting of the corresponding alcohols containing 10% toluene by volume. The activation parameters ΔH≠ and ΔS≠ have been calculated and an interpretation of them is given in terms of solvation effects during the activation process. A comparison between the activation parameters for proton transfers and E2 olefin-forming β-elimination reactions is made and discussed with respect to transition state character of the latter reactions.

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