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Iron Olefin Metathesis: Unlocking Reactivity and Mechanistic Insights

Zachary S. Lincoln, Vlad M. Iluc

2024Journal of the American Chemical Society14 citationsDOI

Abstract

Olefin metathesis catalyzed by iron complexes has garnered substantial interest due to iron’s abundance and nontoxicity relative to ruthenium, yet its full potential remains untapped, largely because of the propensity of iron carbenes to undergo cyclopropanation instead of cycloreversion from a metallacycle intermediate. In this report, we elucidate the reactions of [{PC(sp 2 )P}Fe(L)(N 2 )], ([PC(sp 2 )P] = bis[2-(diisopropylphosphino)phenyl]methylene) with strained olefins, unveiling their capability to yield metathesis-related products. Our investigations led to the isolation of a structurally characterized metallacyclobutane during the reaction with norbornadiene derivatives, ultimately leading to a ring-opened iron alkylidene. These findings provide compelling evidence that iron complexes adhere to the Chauvin olefin metathesis mechanism.

Topics & Concepts

ChemistryCyclopropanationOlefin metathesisMetathesisRutheniumSalt metathesis reactionReactivity (psychology)MetallacycleOlefin fiberMethyleneNorbornadieneCatalysisCombinatorial chemistryOrganic chemistryPolymerizationOpticsX-ray crystallographyPhysicsDiffractionMedicineAlternative medicinePathologyPolymerSynthetic Organic Chemistry MethodsOrganometallic Complex Synthesis and CatalysisCyclopropane Reaction Mechanisms
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