What is the stabilizing interaction with nucleophilic solvents in the transition state for solvolysis of tertiary derivatives: nucleophilic solvent participation or nucleophilic solvation?
[structure: see text] We propose that controversy concerning the mechanism for solvolysis at tertiary carbon is semantic and can be avoided by making a clear distinction between (1) nucleophilic solvent participation, which is stabilization of the transition state for concerted solvolysis by formation of a partial covalent bond to the solvent nucleophile, and (2) nucleophilic solvation, which is stabilization of the transition state for stepwise solvolysis through carbocation or ion pair intermediates by charge-dipole interactions with nucleophilic solvents.
Richard
J P
JP
Department of Chemistry, University at Buffalo, SUNY, Buffalo, New York 14260-3000, USA. jrichard@chem.buffalo.edu
Toteva
M M
MM
Amyes
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TL
D002384:Catalysis; D055598:Chemical Phenomena; D002627:Chemistry, Physical; D006843:Hydrocarbons, Chlorinated / Q000737:chemistry*; D015394:Molecular Structure; D012997:Solvents; D013329:Structure-Activity Relationship
D006843:Hydrocarbons, Chlorinated; D012997:Solvents