Theory of Organic Reactions by Nicolaos Demetrios Epiotis (auth.)

By Nicolaos Demetrios Epiotis (auth.)

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Aj Stereochemistry. This term refers to the geometrical change within one or both reactants, such as bond rotation or inversion of configuration of an atomic center. We can distinguish three different types of reactions: 1. Reactions where both reactants undergo bond rotation or inversion. These will be designated T+T+ reactions. 2. Reactions where one reactant undergoes rotation or inversion but the other does not. These will be designated T+T- reactions. 3. Reactions where neither reactant undergoes rotation or inversion.

30 3. E. surfaces for representative organic reactions. These surfaces can provide direct information about many aspects of chemical reactivity. Attention is focused primarily on the following reaction features: a) b) c) d) e) f) Stereochemistry. Regiochemistry. Topochemistry. The effect of substituents on reaction rate. The selectivity-polarity relationship. The possible existence of observable or isolable intermediates. Accordingly, it is essential that we define the meaning of the above terms.

R tllie = 0,tlP > 0 (c) Fig. 13. Different patterns of noncrossing diabatic surface interactions. Diabatic surfaces are indicated by solid lines and adiabatic surfaces by dashed lines 4>, ____ -,,;/ / I I "'2~ "'. "'. E4>~ E4>~ '" .............. _---r Fig. 14. a) Energy gap control of diabatic surface interaction. b) Matrix element control of diabatic surface interaction. P < O. P negative, the result will depend on the exact magnitude of the two quantities. P I, the question of energy gap control or matrix element control may arise [21].

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