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Steric effects on reaction rates. XI. Solvolysis of tertiary carbon substrates rationalized by molecular mechanics calculations
Author(s) -
Müller Paul,
Mareda Jiri
Publication year - 1989
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.540100702
Subject(s) - solvolysis , steric effects , chemistry , reactivity (psychology) , computational chemistry , molecular mechanics , medicinal chemistry , organic chemistry , hydrolysis , molecular dynamics , medicine , alternative medicine , pathology
The steric energy difference (Δ E st ) 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 bridge‐head substrates are included in the plot. However, the quality of the fit is better for bridgehead substrates alone.