Reactivity selectivity principle

Radical additions lo double bonds are, in general, highly exothermic processes and rates increase with increasing temperature. The rcgiospccificity of addition to double bonds and the relative reactivity of various olefins towards radicals are also temperature dependent. Typically, specificity decreases with increasing temperature (the Reactivity-Selectivity Principle applies). However, a number of exceptions to this general rule have been reported. 8 63... 

Reaction scheme, defined, 9 Reactions back, 26 branching, 189 chain, 181-182, 187-189 competition, 105. 106 concurrent, 58-64 consecutive, 70, 130 diffusion-controlled, 199-202 elementary, 2, 4, 5, 12, 55 exchange, kinetics of, 55-58, 176 induced, 102 opposing, 49-55 oscillating, 190-192 parallel, 58-64, 129 product-catalyzed, 36-37 reversible, 46-55 termination, 182 trapping, 2, 102, 126 Reactivity, 112 Reactivity pattern, 106 Reactivity-selectivity principle, 238 Relaxation kinetics, 52, 257 -260 Relaxation time, 257 Reorganization energy, 241 Reversible reactions, 46-55 concentration-jump technique for, 52-55... 

This Lewis acid ability of increasing both the reaction rate and the selectivity of the cycloaddition is surprising, since in other catalyzed reactions an increase in the reaction rate is accompanied by a decreased selectivity according to the reactivity selectivity principle. This apparently contradictory behavior of the Lewis acids has been explained theoretically [6,7]. 

In other words, under these restrictive conditions, outer sphere electron-transfer reactions obeying the Marcus-Hush model are typical examples where the Hammond-Leffler postulate and the reactivity-selectivity principle (see, for example, Pross, 1977, and references cited therein, for the definition of these notions) are expected to apply. 

In this instance, not only do the calculations bring into question the validity (or at least the generality) of the reactivity-selectivity principle but, more importantly, they open up a route to actually improving reaction selectivity. Note, in particular, the close parallels between the way this investigation was carried out and the way in which an experimental study would be performed. 

The roles of carbocations in commercially important hydrocarbon transformations are still not perfectly understood. The same can be said for carbocations in biological systems. Significant questions concerning reactivity still need to be explained. Why do so many reactions of carbocations show constant selectivity, in violation of the reactivity-selectivity principle Is it possible to develop a unified scale of elec-trophilicity-nucleophilicity, in particular one that incorporates these parameters into the general framework of Lewis acidity and basicity. Finally, quite sophisticated synthetic transformations are being developed that employ carbocations, based upon insights revealed by the mechanistic studies. 

Reactivity of X. The more reactive Cl- is less selective and more influenced by the probability factor. The less reactive Br- is more selective and less influenced by the probability factor. As summarized by the reactivity-selectivity principle If the attacking species is more reactive, it will be less selective, and the yields will be closer to those expected from the probability factor. 

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