Solvolysis is accelerated when a suitably aligned neighbouring π or strained σ bond stabilizes the developing cation. T has the strongest favourable π participation; R benefits from cyclopropane σ participation; Q also has π assistance but a less favourable geometric relationship. S has less assistance, and P has the most difficult unassisted bridge-position ionization. Comparing those stabilization and alignment effects gives T > R > Q > S > P, A.
More Reaction Mechanisms: Basic mechanistic concepts and energy profile diagrams - kinetics versus thermodynamic control, Hammond’s postulate and Curtin-Hammett principle. Methods of determining reaction mechanisms through kinetics, identification of products, intermediates and isotopic labelling. Solvent effects in substitution and elimination reactions. Linear free-energy relationship – Hammett and Taft equations. questions
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