A DFT Study on FeI/FeII/FeIII Mechanism of the Cross-Coupling between Haloalkane and Aryl Grignard Reagent Catalyzed by Iron-SciOPP Complexes.

ABSTRACT: To explore plausible reaction pathways of the cross-coupling reaction between a haloalkane and an aryl metal reagent catalyzed by an iron-phosphine complex, we examine the reaction of FeBrPh(SciOPP) 1 and bromocycloheptane employing density functional theory (DFT) calculations. Besides the cross-coupling, we also examined the competitive pathways of ?-hydrogen elimination to give the corresponding alkene byproduct. The DFT study on the reaction pathways explains the cross-coupling selectivity over the elimination in terms of FeI/FeII/FeIII mechanism which involves the generation of alkyl radical intermediates and their propagation in a chain reaction manner. The present study gives insight into the detailed molecular mechanic of the cross-coupling reaction and revises the FeII/FeII mechanisms previously proposed by us and others.

SUBMITTER: Sharma AK 

PROVIDER: S-EPMC7465158 | biostudies-literature | 2020 Aug

REPOSITORIES: biostudies-literature