What Is the Stabilizing Interaction with Nucleophilic Solvents in the Transition State for Solvolysis of Tertiary Derivatives: Nucleophilic Solvent Participation or Nucleophilic Solvation?

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Abstract

[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.

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