Two-State Reactivity in Iron-Catalyzed Alkene Isomerization Confers σ-Base Resistance
Sean A. Lutz, Anne K. Hickey, Yafei Gao, Chun‐Hsing Chen, Jeremy M. Smith
Abstract
A low-coordinate, high spin (S = 3/2) organometallic iron(I) complex is a catalyst for the isomerization of alkenes. A combination of experimental and computational mechanistic studies supports a mechanism in which alkene isomerization occurs by the allyl mechanism. Importantly, while substrate binding occurs on the S = 3/2 surface, oxidative addition to an η1-allyl intermediate only occurs on the S = 1/2 surface. Since this spin state change is only possible when the alkene substrate is bound, the catalyst has high immunity to typical σ-base poisons due to the antibonding interactions of the high spin state.
Topics & Concepts
ChemistryIsomerizationAlkeneCatalysisReactivity (psychology)PhotochemistrySubstrate (aquarium)Organic chemistryOceanographyGeologyMedicinePathologyAlternative medicineMetal-Catalyzed Oxygenation MechanismsOrganometallic Complex Synthesis and CatalysisAsymmetric Hydrogenation and Catalysis