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How the Lewis Base F^- Catalyzes the 1,3-Dipolar Cycloaddition between Carbon Dioxide and Nitrilimines.

ABSTRACT: The mechanism of the Lewis base F^- catalyzed 1,3-dipolar cycloaddition between CO₂ and nitrilimines is interrogated using DFT calculations. F^- activates the nitrilimine, not CO₂ as proposed in the literature, and imparts a significant rate enhancement for the cycloaddition. The origin of this catalysis is in the strength of the primary orbital interactions between the reactants. The Lewis base activated nitrilimine-F^- has high-lying filled FMOs. The smaller FMO-LUMO gap promotes a rapid nucleophilic attack and overall cycloaddition with CO₂.

SUBMITTER: Svatunek D

PROVIDER: S-EPMC8023701 | biostudies-literature |

REPOSITORIES: biostudies-literature

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