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Energy diagrams showing how to interpret Hammond's Postulate. In case (a), which is an exothermic reaction, the energy of the transition state is closer in energy to that of the reactant than that of the intermediate or the product. Therefore, from the postulate, the structure of the transition state also more closely resembles that of the ...
The IUPAC acknowledges the three divergent definitions of carbonium ion and urges care in the usage of this term. For the remainder of this article, the term carbonium ion will be used in this latter restricted sense, while non-classical carbocation will be used to refer to any carbocation with C–C and/or C–H σ-bonds delocalized by bridging.
In 1962, Edwards and Pearson (the latter of HSAB theory) introduced the phrase alpha effect for this anomaly. He offered the suggestion that the effect was caused by a transition state (TS) stabilization effect: on entering the TS the free electron pair on the nucleophile moves away from the nucleus, causing a partial positive charge which can be stabilized by an adjacent lone pair as for ...
An example of the monovalent carbocation. A pyramidal carbocation is a type of carbocation with a specific configuration. This ion exists as a third class, besides the classical and non-classical ions. In these ions, a single carbon atom hovers over a four- or five-sided polygon, in effect forming a pyramid. The four-sided pyramidal ion will ...
Radicals decrease in stability as they are closer to the nucleus, because the electron affinity of the orbital increases. As a general rule, hybridizations minimizing s-character increase the stability of radicals, and decreases the bond dissociation energy (i.e. sp 3 hybridization is most stabilizing). [6]
The ability of polar solvents to increase the rate of S N 1 reactions is a result of the polar solvent's solvating the reactant intermediate species, i.e., the carbocation, thereby decreasing the intermediate energy relative to the starting material.
This regioselectivity is rationalized by the resonance stabilization of a neighboring carbocation by a lone pair on the initially installed halogen. Depending on relative rates of the two steps, it may be difficult to stop at the first stage, and often, mixtures of the mono and bis hydrohalogenation products are obtained.
Stabilization is ranked the order, -F < -Cl < -CH 3 < -CH=CH 2. All substituents impart stability except for fluorine which destabilized the vinyl cation by 7 kcal/mole. This phenomenon can be explained by comparing a-fluorine substituent effects on vinyl and ethyl cations. In ethyl cations, fluorine stabilizes the carbocation.