Formation and stability of carbocations and carbanions in water and intrinsic barriers to their reactions

Accounts of Chemical Research

Volumn 34, Issue 12, 2001, Pages 981-988

  Richard, J P ^a   Amyes, T L ^a   Toteva, M M ^a  

^a UNIVERSITY AT BUFFALO   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ANION; CARBON; CATION; ORGANIC COMPOUND; SOLVENT; WATER;

ARTICLE; CHEMICAL REACTION; CHEMICAL REACTION KINETICS; CHEMICAL STRUCTURE; CHEMISTRY; EQUILIBRIUM CONSTANT; KINETICS; MOLECULAR INTERACTION; REACTION ANALYSIS; SYNTHESIS; THERMODYNAMICS; REVIEW;

ANIONS; CARBON; CATIONS; KINETICS; ORGANIC CHEMICALS; SUPPORT, NON-U.S. GOV'T; SUPPORT, U.S. GOV'T, P.H.S.; THERMODYNAMICS;

EID: 0035543101     PISSN: 00014842     EISSN: None     Source Type: Journal    
DOI: 10.1021/ar0000556     Document Type: Article

References (43)

1. How does a reaction choose its mechanism?
2. Flash photolysis generation and reactivities of carbenium ions and nitrenium ions
3. Enols and other reactive species
4. Formation and stability of ring-substituted 1-phenylethyl carbocations
5. The extraordinarily long lifetimes and other properties of highly destabilized ring-substituted 1-phenyl-2,2,2-trifluoroethyl carbocations
6. Direct observation of β-fluoro-substituted 4-methoxyphenethyl cations by laser flash photolysis
7. Experiments and calculations for determination of the stabilities of benzyl, benzhydryl, and fluorenyl carbocations: Antiaromaticity revisited
8. The effects of α-substituents on the kinetic and thermodynamic stability of 4-methoxybenzyl carbocations: Carbocation lifetimes that are independent of their thermodynamic stability
9. Reactions of substituted 1-phenylethyl carbocations with alcohols and other nucleophilic reagents
10. Dynamics for reaction of an ion pair in aqueous solution: The rate constant for ion pair reorganization
11. Dynamics for reaction of an ion pair in aqueous solution: Reactivity of carboxylate anions in bimolecular carbocation-nucleophile addition and unimolecular ion pair collapse
12. Experimental and computational determination of the effect of the cyano group on carbon acidity in water
13. Formation and stability of organic zwitterions in aqueous solution: Enolates of the amino glycine and its derivatives
14. α of ethyl acetate: Broønsted correlation for deprotonation of a simple oxygen ester in aqueous solution
15. Formation and stability of enolates of acetamide and acetate ion: An eigen plot for proton transfer at α-carbonyl carbon
16. Proton transfer, acid-base catalysis, and enzymatic hydrolysis
17. Generation and stability of a simple thiol ester enolate in aqueous solution
18. Biological enolates: Generation and stability of the enolate of N-protonated glycine methyl ester in water
19. Chemistry of conjugate anions and enols. IV. The kinetically controlled enolization of α,β-unsaturated ketones and the nature of the transition state
20. Theoretical relations among rate constants, barrier, and broønsted slopes of chemical reactions
21. Unusual slopes of free energy plots in kinetics
22. Structure-reactivity relationships and intrinsic reaction barriers for nucleophile additions to a quinone methide: A strongly resonance-stabilized carbocation
23. The principle of nonperfect synchronization: More than a qualitative concept?
24. The nitroalkane anomaly
25. Lifetimes of oxocarbenium ions in aqueous solution from common ion inhibition of the solvolysis of α-Azido ethers by added azide ion
26. Effects of electronic geminal interactions on the solvolytic reactivity of methoxymethyl derivatives
27. Structure-reactivity relationships for addition of sulfur nucleophiles to electrophilic carbon: Resonance, polarization, and steric/electrostatic effects
28. A consideration of the barrier for carbocation-nucleophile combination reactions
29. Effect of β-fluorine substituents on the rate and equilibrium constants for the reactions of α-substituted 4-methoxybenzyl carbocations and on the reactivity of a simple quinone methide
30. Generation and determination of the lifetime of an α-carbonyl substituted carbocation
31. How does organic structure determine organic reactivity? Nucleophilic substitution and alkene-forming elimination reactions of α-carbonyl and α-thiocarbonyl substituted benzyl derivatives
32. Theoretical studies of the effects of α-substituents on the resonance demand of 4-methoxybenzyl carbocations
33. Kinetic and thermodynamic stabilities of α-oxygen- and α-sulfur-stabflized carbocations in solution
34. Spontaneous cleavage of gem-Diazides: A comparison of the effects of α-azido and other electron-donating groups on the kinetic and thermodynamic stability of benzyl and alkyl carbocations in aqueous solution
35. A systematic survey of the effects of substituents on the structures and energies of the principal organic reaction intermediates
36. Cyanocarbon acids: Direct evidence that their ionization is not an encounter-controlled process and rationalization of the unusual solvent isotope effects
37. Is the acetate anion stabilized by resonance or electrostatics? A systematic structural comparison
38. Carbanions 2. Intramolecular interactions in carbanions stabilized by carbonyl, cyano, isocyano, and nitro groups
39. Mechanisms for the uncatalyzed and hydrogen ion catalyzed reactions of a simple quinone methide with solvent and halide ions
40. Mechanism of reactions of N-(methoxymethyl)-N, N-dimethylanilinium ions with nucleophilic reagents
41. Intrinsic barriers for the reactions of an oxocarbenium ion in water
42. Mechanistic imperatives for catalysis of aldol addition reactions: Partitioning of the enolate intermediate between reaction with broønsted acids and the carbonyl group