Bimolecular Reductive Elimination of Ethane from Pyridine(diimine) Iron Methyl Complexes: Mechanism, Electronic Structure, and Entry into [2+2] Cycloaddition Catalysis

Kovel, Carli B.; Darmon, Jonathan M.; Stieber, S. Chantal E.; Pombar, Gisselle; Pabst, Tyler P.; Theis, Bastian; Turner, Zoë R.; Üngör, Ökten; Shatruk, Michael; DeBeer, Serena; Chirik, Paul J.

doi:10.1021/jacs.2c10547

Title: Bimolecular Reductive Elimination of Ethane from Pyridine(diimine) Iron Methyl Complexes: Mechanism, Electronic Structure, and Entry into [2+2] Cycloaddition Catalysis

Journal Article · Thu Feb 23 00:00:00 EST 2023 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.2c10547· OSTI ID:1958554

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Princeton Univ., NJ (United States)
Florida State Univ., Tallahassee, FL (United States)
Max Planck Inst. for Chemical Energy Conversion, Mülheim an der Ruhr (Germany)

The application of bimolecular reductive elimination to the activation of iron catalysts for alkene–diene cycloaddition is described. Key to this approach was the synthesis, characterization, electronic structure determination, and ultimately solution stability of a family of pyridine(diimine) iron methyl complexes with diverse steric properties and electronic ground states. Both the aryl-substituted, (^MePDI)FeCH₃ and (^EtPDI)FeCH₃ (^RPDI = 2,6-(2,6-R₂-C₆H₃N=CMe)₂C₅H₃N), and the alkyl-substituted examples, (^CyAPDI)FeCH₃ (^CyAPDI = 2,6-(C₆H₁₁N=CMe)₂C₅H₃N), have molecular structures significantly distorted from planarity and S = 3/2 ground states. The related N-arylated derivative bearing 2,6-di-isopropyl aryl substituents, (^iPrPDI)FeCH₃, has an idealized planar geometry and exhibits spin crossover behavior from S = 1/2 to S = 3/2 states. At 23 °C under an N₂ atmosphere, both (^MePDI)FeCH₃ and (^EtPDI)FeCH₃ underwent reductive elimination of ethane to form the iron dinitrogen precatalysts, [(^MePDI)Fe(N₂)]₂(μ-N₂) and [(^EtPDI)Fe(N₂)]₂(μ-N₂), respectively, while (^iPrPDI)FeCH₃ proved inert to C–C bond formation. By contrast, addition of butadiene to all three iron methyl complexes induced ethane formation and generated the corresponding iron butadiene complexes, (^RPDI)Fe(η⁴-C₄H₆) (R = Me, Et, ⁱPr), known precatalysts for the [2+2] cycloaddition of olefins and dienes. Kinetic, crossover experiments, and structural studies were combined with magnetic measurements and Mössbauer spectroscopy to elucidate the electronic and steric features of the iron complexes that enable this unusual reductive elimination and precatalyst activation pathway. Furthermore, transmetalation of methyl groups between iron centers was fast at ambient temperature and independent of steric environment or spin state, while the intermediate dimer underwent the sterically controlled rate-determining reaction with either N₂ or butadiene to access a catalytically active iron compound.

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Research Organization:: Princeton Univ., NJ (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0022303

OSTI ID:: 1958554

Journal Information:: Journal of the American Chemical Society, Vol. 145, Issue 9; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Alkyls
Butadiene
Hydrocarbons
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Reductive elimination

CCDC 2181969: Experimental Crystal Structure Determination B., Kovel, Carli; M., Darmon, Jonathan; E., Stieber, S. Chantal https://doi.org/10.5517/ccdc.csd.cc2c7j38 The current record is supplemented by this dataset	dataset	January 2023
CCDC 2226813: Experimental Crystal Structure Determination B., Kovel, Carli; M., Darmon, Jonathan; E., Stieber, S. Chantal https://doi.org/10.5517/ccdc.csd.cc2dr5p1 The current record is supplemented by this dataset	dataset	January 2023
CCDC 2181966: Experimental Crystal Structure Determination B., Kovel, Carli; M., Darmon, Jonathan; E., Stieber, S. Chantal https://doi.org/10.5517/ccdc.csd.cc2c7j05 The current record is supplemented by this dataset	dataset	January 2023
CCDC 2181965: Experimental Crystal Structure Determination B., Kovel, Carli; M., Darmon, Jonathan; E., Stieber, S. Chantal https://doi.org/10.5517/ccdc.csd.cc2c7hz3 The current record is supplemented by this dataset	dataset	January 2023
CCDC 2181967: Experimental Crystal Structure Determination B., Kovel, Carli; M., Darmon, Jonathan; E., Stieber, S. Chantal https://doi.org/10.5517/ccdc.csd.cc2c7j16 The current record is supplemented by this dataset	dataset	January 2023
CCDC 2226812: Experimental Crystal Structure Determination B., Kovel, Carli; M., Darmon, Jonathan; E., Stieber, S. Chantal https://doi.org/10.5517/ccdc.csd.cc2dr5n0 The current record is supplemented by this dataset	dataset	January 2023
CCDC 2181968: Experimental Crystal Structure Determination B., Kovel, Carli; M., Darmon, Jonathan; E., Stieber, S. Chantal https://doi.org/10.5517/ccdc.csd.cc2c7j27 The current record is supplemented by this dataset	dataset	January 2023

Title: Bimolecular Reductive Elimination of Ethane from Pyridine(diimine) Iron Methyl Complexes: Mechanism, Electronic Structure, and Entry into [2+2] Cycloaddition Catalysis

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