Mechanistic insight from activation parameters for the reaction between co-enzyme B12 and cyanide: further evidence that heterolytic Co–C bond cleavage is solvent-assistedElectronic supplementary information (ESI) available: NMR and kinetic data. See http://www.rsc.org/suppdata/dt/b2/b210068a/

2003 ◽  
pp. 596-602 ◽  
Author(s):  
Mohamed S. A. Hamza ◽  
Andrew G. Cregan ◽  
Nicola E. Brasch ◽  
Rudi van Eldik
Keyword(s):  
Kinetic Data ◽  
Bond Cleavage ◽  
Activation Parameters ◽  
Supplementary Information ◽  
Mechanistic Insight

scholarly journals Ruthenium-catalyzed cascade C–H activation/annulation of N-alkoxybenzamides: reaction development and mechanistic insight

2020 ◽  
Vol 11 (42) ◽  
pp. 11562-11569
Author(s):  
Liangliang Song ◽  
Xiaoyong Zhang ◽  
Xiao Tang ◽  
Luc Van Meervelt ◽  
Johan Van der Eycken ◽  
...  
Keyword(s):  
Bond Cleavage ◽  
Mechanistic Insight ◽  
Alkyne Insertion

A highly selective ruthenium-catalyzed C–H activation/annulation through a pathway involving N–O bond cleavage prior to alkyne insertion is developed.

scholarly journals Kinetics and mechanism of the C-S coupling reactions of aryl Grignard reagents with aryl arenesulfonates

2008 ◽  
Vol 6 (2) ◽  
pp. 237-244 ◽  
Author(s):  
Ender Erdik ◽  
Fatma Eroğlu
Keyword(s):  
Nucleophilic Addition ◽  
Kinetic Data ◽  
Grignard Reagent ◽  
Activation Parameters ◽  
Grignard Reagents ◽  
Coupling Reactions ◽  
Sulfonyl Group ◽  
First Order ◽  
Kinetics Of ◽  
Hammett Relationship

AbstractThe kinetics of the C-S coupling of arylmagnesium bromides with phenyl tosylate has been studied in THF: toluene at 90°C. The reaction is first order in Grignard reagent and first order in phenyl tosylate. Kinetic data, Hammett relationship and activation parameters are consistent with a nucleophilic addition mechanism involving rate determining attack of carbanion to sulfonyl group followed by a fast phenoxide group leaving.

scholarly journals Kinetics of solvolysis in water of four secondary alkyl nitrates

1982 ◽  
Vol 60 (13) ◽  
pp. 1780-1785 ◽  
Author(s):  
Ross Elmore Robertson ◽  
Kalvelil Matthew Koshy ◽  
Adrianne Annessa ◽  
Jan N. Ong ◽  
John Marshall William Scott ◽  
...  
Keyword(s):  
Heat Capacity ◽  
Rate Constant ◽  
Analytical Methods ◽  
Kinetic Data ◽  
Activation Parameters ◽  
Single Step ◽  
Alkyl Nitrates ◽  
Two Stage ◽  
Kinetics Of ◽  
Single Step Reaction

Kinetic data are reported for the solvolysis in water of propane-2-nitrate, butane-2-nitrate, cyclopentyl nitrate, and cyclohexyl nitrate. In each case, the dependence of rate constant on temperature is analysed in terms of two mechanisms for the solvolytic reaction. First it is assumed that the rate constant describes a single step reaction, the analysis leading to estimates of the heat capacity of activation ΔCp≠. Three different analytical methods are discussed in this regard. Second it is assumed that the rate constant describes a two stage mechanism, the first stage being reversible. In this case the explanation of the ΔCp≠ term calculated according to the first mechanism is quite different. We comment on the alternative explanations of trends in activation parameters.

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