Mechanistic Features in Al(I)-Mediated Oxidative Addition of Aryl C-F Bonds: Insights From Density Functional Theory Calculations.

ABSTRACT: The oxidative addition of a range of robust aryl C-F bonds to a single Al(I) center supported by a (NacNac)^- bidentate ligand ((NacNac)^- = [ArNC(Me)CHC(Me)NAr]^- and Ar = 2,6- Pr 2 i C₆H₃) have been explored by density functional theory calculations. Our calculations demonstrate that the Al(I) center-mediated C-F insertion generally proceeds via the concerted mechanism that involve both the donation ( n Al → σ C - F * ) and back-donation ( σ F ( p ) → π Al ( p ) * ) interactions. In addition, the predicted free energy barriers for the C-F bond activation show good agreement with the experimental information available. Finally, the comparative studies show that B(I) is the most active among group III metals (B, Al, Ga

SUBMITTER: Zhang X 

PROVIDER: S-EPMC6733912 | biostudies-literature | 2019

REPOSITORIES: biostudies-literature