Reaction mechanism of acetonitrile, olefins, and amines catalyzed by Ag2CO3: A DFT investigation

The mechanism of Ag2CO3‐catalyzed reactions of acetonitrile, olefins, and amines was investigated by using the M06‐L‐D3/6‐311 + G(d,p) method and level, and solvation model based on solute electron density (SMD) model was applied to simulate the solvent effect. Calculations show that the Ag2CO3 coul...

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Bibliographic Details
Published inJournal of physical organic chemistry Vol. 37; no. 3
Main Authors Chen, Bin, Da‐Gang Zhou, Li‐Jun Yang
Format Journal Article
LanguageEnglish
Published Bognor Regis Wiley Subscription Services, Inc 01.03.2024
Subjects
Acetonitrile
Alkenes
Amines
Benzene
Chemical reactions
Electron density
Electron spin
Electron transfer
Electrons
Reaction mechanisms
Shift reaction
Single electrons
Solvation
Solvent effect
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Summary:The mechanism of Ag2CO3‐catalyzed reactions of acetonitrile, olefins, and amines was investigated by using the M06‐L‐D3/6‐311 + G(d,p) method and level, and solvation model based on solute electron density (SMD) model was applied to simulate the solvent effect. Calculations show that the Ag2CO3 could achieve the Csp3‐H activation by coordinating with the terminal nitrogen atom of CH3CN; then, the addition reaction happened between the obtained Ag‐complex intermediate and olefin via the coordination of Ag and benzene ring; finally, the obtained radical intermediate continues to go through one single electron transfer (SET) process, addition reaction, and H‐shift reaction to yield the final product. The computational results reveal that Fe3+ cation would have assisted the SET process successfully and the path of direct addition with the amine is the optimal. Fukui function and dual descriptor can be used to predict the reactive sites, and electron spin density isosurface graphs can analyze the structures and reveal the substances.
ISSN:0894-3230
1099-1395
DOI:10.1002/poc.4594