Document Detail


Formation and stability of carbocations and carbanions in water and intrinsic barriers to their reactions.
MedLine Citation:
PMID:  11747416     Owner:  NLM     Status:  MEDLINE    
Abstract/OtherAbstract:
Lifetimes in water as short as 10(-11) s have been determined for carbocations and carbanions by referencing the rate of their reaction with solvent species to that for the appropriate "clock" reaction, and equilibrium constants have been determined as the ratio of rate constants for their formation and breakdown. Rate-equilibrium correlations for these organic ions are often poor and sometimes even defy the simple generalization that reactivity increases with decreasing stability. This seemingly confusing body of data can be understood through consideration of the both the Marcus intrinsic barrier and the thermodynamic driving force to reaction of these organic ions.
Authors:
J P Richard; T L Amyes; M M Toteva
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Publication Detail:
Type:  Journal Article; Research Support, Non-U.S. Gov't; Research Support, U.S. Gov't, P.H.S.; Review    
Journal Detail:
Title:  Accounts of chemical research     Volume:  34     ISSN:  0001-4842     ISO Abbreviation:  Acc. Chem. Res.     Publication Date:  2001 Dec 
Date Detail:
Created Date:  2001-12-18     Completed Date:  2002-01-31     Revised Date:  2007-11-14    
Medline Journal Info:
Nlm Unique ID:  0157313     Medline TA:  Acc Chem Res     Country:  United States    
Other Details:
Languages:  eng     Pagination:  981-8     Citation Subset:  IM    
Affiliation:
Department of Chemistry, University at Buffalo, State University of New York, Buffalo, New York 14260-3000, USA. jrichard@chem.buffalo.edu
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MeSH Terms
Descriptor/Qualifier:
Anions
Carbon / chemistry
Cations
Kinetics
Organic Chemicals / chemistry*
Thermodynamics
Grant Support
ID/Acronym/Agency:
GM39754/GM/NIGMS NIH HHS
Chemical
Reg. No./Substance:
0/Anions; 0/Cations; 0/Organic Chemicals; 7440-44-0/Carbon

From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine


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