A DFT Study on Fe<sup>I</sup>/Fe<sup>II</sup>/Fe<sup>III</sup> Mechanism of the Cross-Coupling between Haloalkane and Aryl Grignard Reagent Catalyzed by Iron-SciOPP Complexes
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) <b>1</b> and bromocycloheptane employing density functional theory (DFT) calculations. Be...
| Main Authors: | , |
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| Format: | Article |
| Language: | English |
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MDPI AG
2020-08-01
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| Series: | Molecules |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1420-3049/25/16/3612 |
| Summary: | 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) <b>1</b> and bromocycloheptane employing density functional theory (DFT) calculations. Besides the cross-coupling, we also examined the competitive pathways of β-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 Fe<sup>I</sup>/Fe<sup>II</sup>/Fe<sup>III</sup> 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 Fe<sup>II</sup>/Fe<sup>II</sup> mechanisms previously proposed by us and others. |
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| ISSN: | 1420-3049 |