✦ LIBER ✦
Steric effects on reaction rates. XI. Solvolysis of tertiary carbon substrates rationalized by molecular mechanics calculations
✍ Scribed by Paul Müller; Jiri Mareda
- Book ID
- 102306345
- Publisher
- John Wiley and Sons
- Year
- 1989
- Tongue
- English
- Weight
- 498 KB
- Volume
- 10
- Category
- Article
- ISSN
- 0192-8651
No coin nor oath required. For personal study only.
✦ Synopsis
The steric energy difference (A&) between tertiary carbenium ions (R') and the corresponding alcohols has been calculated by MM2 for a series of tertiary nonbridgehead substrates and correlated with their rate of solvolytic reactivity. Satisfactory correlation is obtained, except for p-nitrobenzoates of highly congested substrates. The slope and intercept of the correlations remain almost unchanged if bridgehead substrates are included in the plot. However, the quality of the fit is better for bridgehead substrates alone.