- Reactivity–selectivity principle
chemistrythe reactivity–selectivity principle or RSP states that a more reactive chemical compoundor reactive intermediateis less selective in chemical reactions. In this context selectivity represents the ratio of reaction rates.
This principle was generally accepted until the 1970s when too many exceptions started to appear. The principle is now considered obsolete ["Minireview The Reactivity-Selectivity Principle: An Imperishable Myth in Organic Chemistry " Herbert Mayr, Armin R. Ofial
Angewandte Chemie International EditionVolume 45, Issue 12 , Pages 1844 - 1854 [http://dx.doi.org/10.1002/anie.200503273 Abstract] ] .
A classic example of perceived RSP found in older organic textbooks concerns the
free radical halogenationof simple alkanes. Whereas the relatively unreactive brominereacts with 2-methylbutane predominantly to 2-bromo-2-methylbutane, the reaction with much more reactive chlorineresults in a mixture of all four regioisomers.
Another example of RSP can be found in the selectivity of the reaction of certain
carbocations with azides and water. The very stable triphenylmethyl carbocation derived from solvolysisof the corresponding triphenylmethylchloride reacts a 100 times faster with the azide anion than with water. When the carbocation is the very reactive tertiary adamantanecarbocation (as judged from diminished rate of solvolysis) this difference is only a factor of 10.
Constant or inverse relationships are just as frequent. For example a group of 3- and 4-substituted
pyridines in their reactivity quantified by their pKashow the same selectivity in their reactions with a group of alkylating reagents.
The reason for the early success of RSP was that the experiments involved very reactive intermediates with reactivities close to
kinetic diffusion controland as a result the more reactive intermediate appeared to react slower with the faster substrate.
General relationships between reactivity and selectivity in chemical reactions can successfully explained by the
The sulfur radical was found to be more reactive (6*108 vs. 1*107 mole-1.s-1) and less selective (selectivity ratio's 76 vs 1200) than the carbon radical. In this case the effect can be explained by extending the
Bell–Evans–Polanyi principlewith a factor accounting for transfer of charge from the reactants to the transition stateof the reaction which can be calculated in silico:
activation energyand the reaction enthalpychange. With the electrophilic sulfur radical the charge transfer is largest with electron-rich alkenes such as acrylonitrile but the resulting reduction in activation energy (β is negative) is offset by a reduced enthalpy. With the nucleophilic carbon radical on the other hand both enthalpy and polar effects have the same direction thus extending the activation energy range.
* Reactivity–selectivity principle
Gold Book[http://www.iupac.org/goldbook/R05186.pdf Link]
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