Abstract
AbstractThe reactivity‐selectivity principle (RSP), which describes a linear relationship between the decrease in selectivity and increase in reactivity of molecules Xm in their reactions with Y1 and Y2, has been much criticized during the last few years. The present paper shows the kind of reactions where the RSP does not hold and reveals how the individual types of reaction can be distinguished by varying the solvent. The dependence of molecule selectivity on temperature produces a further effect. An isoselective relationship (ISR) can be deduced when this dependence is taken into account. This relationship is not concerned with the connection between the temperature‐dependent rate and competition constants, but with the connection existing between activation enthalpies and activation entropies, which are temperature‐independent over wide ranges. The application of the ISR to different types of reactions makes it possible to characterize and distinguish between short‐lived intermediates and underlines the significance of the isoselective temperature (Tis) in interpreting the reaction parameters of linear free energy relationships and in planning syntheses.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callMore From: Angewandte Chemie International Edition in English
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
