Study of Solvent Effect on C—H Cleavage Step by Density Functional Theory
The efficiency of C—H activation has been widely studied and proved.8-aminoquinoline mediated C—H activation is the most commonly utilized method.A large number of computational chemistry studies have proved that the powerful electron-donating effect and rigid structure of 8-aminoquinoline guiding group are the key to its efficient reaction.However,the solvent effect related to this system has not been fully interpreted.In this paper,the continuum solvation models of toluene,1,2-dichloroethane,acetone,acetonitrile and dimethyl sulfoxide were selected in order to engage the density functional theory(DFT)calculation of the RDS of the sp3 C—H activation mediated by 8-aminoquinoline guiding group(C—H cleavage step).Finally,it was found that with the increase of solvent polarity,the entropy reduction of the transition state of the C—H cleavage step decreased significantly that caused the reduction of Gibbs free energy barrier,which finally accelerated the reaction.
C—H activationDensity functional theoryGibbs free energy
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