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Iron Catalyzed Double Bond Isomerization: Evidence for an Fe<sup>I</sup>/Fe<sup>III</sup> Catalytic Cycle

Callum R. Woof, Derek J. Durand, Natalie Fey, Emma Richards, Ruth L. Webster

2021Chemistry - A European Journal26 citationsDOIOpen Access PDF

Abstract

Abstract Iron‐catalyzed isomerization of alkenes is reported using an iron(II) β‐diketiminate pre‐catalyst. The reaction proceeds with a catalytic amount of a hydride source, such as pinacol borane (HBpin) or ammonia borane (H 3 N⋅BH 3 ). Reactivity with both allyl arenes and aliphatic alkenes has been studied. The catalytic mechanism was investigated by a variety of means, including deuteration studies, Density Functional Theory (DFT) and Electron Paramagnetic Resonance (EPR) spectroscopy. The data obtained support a pre‐catalyst activation step that gives access to an η 2 ‐coordinated alkene Fe I complex, followed by oxidative addition of the alkene to give an Fe III intermediate, which then undergoes reductive elimination to allow release of the isomerization product.

Topics & Concepts

IsomerizationChemistryCatalysisAlkenePhotochemistryCatalytic cycleAmmonia boraneElectron paramagnetic resonanceBoraneOxidative additionMedicinal chemistryReactivity (psychology)Reductive eliminationDehydrogenationOrganic chemistryAlternative medicineNuclear magnetic resonanceMedicinePhysicsPathologyAsymmetric Hydrogenation and CatalysisOrganometallic Complex Synthesis and CatalysisCarbon dioxide utilization in catalysis
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