Helpful comments from D. Bethell are gratefully acknowledged. s=slope, E=electrophilicity, N=nucleophilicity.
Limitations of the s(E+N) and Related Equations: Solvent Dependence of Electrophilicity†
Article first published online: 9 MAR 2011
Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Angewandte Chemie International Edition
Volume 50, Issue 16, pages 3608–3611, April 11, 2011
How to Cite
Bentley, T. W. (2011), Limitations of the s(E+N) and Related Equations: Solvent Dependence of Electrophilicity. Angew. Chem. Int. Ed., 50: 3608–3611. doi: 10.1002/anie.201005816
- Issue published online: 5 APR 2011
- Article first published online: 9 MAR 2011
- Manuscript Received: 16 SEP 2010
- linear free-energy relationships;
- solvent effects
Solvent matters: Cations are reference substrates in the equation log k=s(E+N); neglect of solvent effects (see picture; TS=transition state) on their electrophilicity (E) leads to unreliable values of the nucleophilicity (N) and slope (s) parameters that characterize nucleophiles (k is the rate constant). Consequently, these parameters are not recommended for a general scale of nucleophilicity as suggested by Mayr and co-workers.