Formation and Stability of Carbocations and Carbanions in Water and Intrinsic Barriers to Their Reactions

详细信息    查看全文

• 作者：John P. Richard ; Tina L. Amyes ; and Maria M. Toteva
• 刊名：Accounts of Chemical Research
• 出版年：2001
• 出版时间：December 2001
• 年：2001
• 卷：34
• 期：12
• 页码：981 - 988
• 全文大小：116K
• 年卷期：v.34,no.12(December 2001)
• ISSN：1520-4898

文摘

Lifetimes in water as short as 10^-11 s have been determined forcarbocations and carbanions by referencing the rate of theirreaction with solvent species to that for the appropriate "clock"reaction, and equilibrium constants have been determined as theratio of rate constants for their formation and breakdown. Rate-equilibrium correlations for these organic ions are often poor andsometimes even defy the simple generalization that reactivityincreases with decreasing stability. This seemingly confusing bodyof data can be understood through consideration of the both theMarcus intrinsic barrier and the thermodynamic driving force toreaction of these organic ions.