Effect of nucleophilic solvent on the kinetic parameters of the reactions of unimolecular heterolysis. Mechanism of the covalent bond heterolysis |
| |
Authors: | G F Dvorko E A Ponomareva |
| |
Institution: | (1) Department of Chemistry, Kakatiya University, Warangal, 506009, India; |
| |
Abstract: | Reactions of unimolecular heterolysis occur through consecutive formation of four ion pairs: contact, spatially separated,
separated by one solvent molecule, and solvent-separated. In the limiting stage, the contact ion pair interacts with the solvent
cavity. Nucleophilic solvation hinders the separation of ions in the transition state. At the heterolysis of secondary substrates
this is compensated by the nucleophilic solvation of the incipient carbocations from the rear and the reaction rate does not
depend on the solvent nucleophilicity. In the case of heterolysis of tertiary substrates, only partial compensation occurs,
and nucleophilic solvent reduces the reaction rate through reducing the activation entropy. |
| |
Keywords: | |
本文献已被 SpringerLink 等数据库收录! |
|