A comparative study on the hydrolysis of acetic anhydride and N,N-dimethylformamide: Kinetic isotope effect, transition-state structure, polarity, and solvent effect

2017 ◽  
Vol 30 (12) ◽  
pp. e3701 ◽  
Author(s):  
William C. Cooper ◽  
Abhinay Chilukoorie ◽  
Suhesh Polam ◽  
Dane Scott ◽  
Floyd Wiseman
Keyword(s):  
Acetic Anhydride ◽  
Comparative Study ◽  
Transition State ◽  
Solvent Effect ◽  
Isotope Effect ◽  
Kinetic Isotope Effect ◽  
State Structure ◽  
Transition State Structure ◽  
Kinetic Isotope ◽  
Hydrolysis Of

Solvent effects on the structure of SN2 transition states

1978 ◽  
Vol 56 (20) ◽  
pp. 2691-2699 ◽  
Author(s):  
Kenneth Charles Westaway
Keyword(s):  
Transition State ◽  
Isotope Effect ◽  
Solvent Effects ◽  
Kinetic Isotope Effect ◽  
Transition States ◽  
State Structure ◽  
Transition State Structure ◽  
Kinetic Isotope ◽  
Wide Range ◽  
Leaving Group

Two research groups have used heavy atom leaving group kinetic isotope effects to determine how the structure of an SN2 transition state is affected by a change in solvent. Two completely different types of behaviour were observed in these studies. In one case, the leaving group kinetic isotope effect, and thus the transition state structure, changed markedly when the solvent was varied over a reasonably narrow range. In the other study, the leaving group kinetic isotope effect (transition state structure) remained constant over a wide range of solvents. A model describing the interaction between solvent molecules and SN2 transition states is developed and a SolvationruleforSN2reactions which rationalizes the different experimental results is explained and justified. Finally, predictions based on the solvation rule are shown to be in agreement with the results of theoretical calculations of solvent effects on SN2 transition states and secondary α deuterium kinetic isotope effect measurements.

Isotope effects in nucleophilic substitution reactions. VI. The effect of ion pairing on the transition state structure of SN2 reactions

1988 ◽  
Vol 66 (5) ◽  
pp. 1263-1271 ◽  
Author(s):  
Kenneth Charles Westaway ◽  
Zhu-Gen Lai
Keyword(s):  
Transition State ◽  
Isotope Effect ◽  
Kinetic Isotope Effect ◽  
Isotope Effects ◽  
Ion Pair ◽  
State Structure ◽  
Transition State Structure ◽  
Substitution Reactions ◽  
Sn2 Reactions ◽  
Kinetic Isotope

Spectroscopic and conductivity studies of sodium thiophenoxide solutions in four different solvents and the secondary α-deuterium kinetic isotope effects found in the presence of 15-crown-5 ether demonstrate that the secondary α-deuterium kinetic isotope effect and transition state structure for the SN2 reaction between sodium thiophenoxide and n-butyl chloride are significantly different, depending on whether the ionic reactant is a solvent-separated ion-pair complex or a free ion. In all three solvents in which the form of the ionic reactant changes, a smaller isotope effect and tighter transition state are found for the reaction with the ion-pair complex.

Isotope effects in nucleophilic substitution reactions X. The effect of changing the nucleophilic atom on ion-pairing in an SN2 reaction

1998 ◽  
Vol 76 (6) ◽  
pp. 758-764 ◽  
Author(s):  
Yao-ren Fang ◽  
Zhu-gen Lai ◽  
Kenneth Charles Westaway
Keyword(s):  
Transition State ◽  
Nucleophilic Substitution ◽  
Isotope Effect ◽  
Kinetic Isotope Effect ◽  
Isotope Effects ◽  
Substituent Effects ◽  
Ion Pairing ◽  
State Structure ◽  
Transition State Structure ◽  
Kinetic Isotope

The effect of ion-pairing in an SN2 reaction is very different when the nucleophilic atom is changed from sulfur to oxygen, i.e., changing the nucleophile from thiophenoxide ion to phenoxide ion. When the nucleophile is sodium thiophenoxide, ion-pairing markedly alters the secondary α -deuterium kinetic isotope effect (transition state structure) and the substituent effect found by changing the para substituent on the nucleophile. When the nucleophile is sodium phenoxide, ion-pairing does not significantly affect the secondary α -deuterium or the chlorine leaving group kinetic isotope effects (transition state structure) or the substituent effects found by changing a para substituent on the nucleophile or the substrate. The different effects of ion-pairing may occur because the electron density on the hard oxygen atom of the sodium phenoxide is not affected significantly by ion-pairing.Key words: nucleophilic substitution, SN2, kinetic isotope effect, transition state, substituent effects, ion-pair.

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