The N ‐Methylpyrrolidone (NMP) Effect in Iron‐Catalyzed Cross‐Coupling with Simple Ferric Salts and MeMgBr
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The use of N ‐methylpyrrolidone (NMP) as a co‐solvent in ferric salt catalyzed cross‐coupling reactions is crucial for achieving the highly selective, preparative scale formation of cross‐coupled product in reactions utilizing alkyl Grignard reagents. Despite the critical importance of NMP, the molecular level effect of NMP on in situ formed and reactive iron species that enables effective catalysis remains undefined. Herein, we report the isolation and characterization of a novel trimethyliron(II) ferrate species, [Mg(NMP) 6 ][FeMe 3 ] 2 ( 1 ), which forms as the major iron species in situ in reactions of Fe(acac) 3 and MeMgBr under catalytically relevant conditions where NMP is employed as a co‐solvent. Importantly, combined GC analysis and 57 Fe Mössbauer spectroscopic studies identified 1 as a highly reactive iron species for the selective formation generating cross‐coupled product. These studies demonstrate that NMP does not directly interact with iron as a ligand in catalysis but, alternatively, interacts with the magnesium cations to preferentially stabilize the formation of 1 over [Fe 8 Me 12 ] − cluster generation, which occurs in the absence of NMP.
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Addition of N-methyl pyrrolidone (NMP), a cyclic tertiary amide, has been shown to enhance the catalytic activity of iron in cross-coupling reactions which enables the formation of catalytically active monomeric ferrates by coordination.
“In fact, the addition of N-methyl pyrrolidone (NMP), a cyclic tertiary amide, has been shown to enhance the catalytic activity of iron in cross-coupling reactions which enables the formation of catalytically active monomeric ferrates by coordination.70–73”
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- Authors
- Muñoz, S. B., Daifuku, S. L., Sears, J. D., Baker, T. M., Carpenter, S. H., Brennessel, W. W., & Neidig, M. L.
- Affiliations
- University of Rochester (US)
- Corresponding author
- Neidig, Michael L.
- ORCID
- Venue
- Angewandte Chemie International Edition
- Publisher
- Wiley
- Published
- 2018-05-08
- Volume
- 57
- Issue
- 22
- Pages
- 6496-6500
- ISSN
- 1433-7851 (ISSN-L)
- 1521-3773
- PMC
- PMC5992103
- OpenAlex
- W2795626882
- Cited by
- 81
- References
- 30
- Citations by year
- 2026: 6 · 2025: 4 · 2024: 9 · 2023: 9 · 2022: 4 · 2021: 10 · 2020: 15 · 2019: 13 · 2018: 11
- FWCI
- 5.02
- Type
- journal article
- Language
- en
- Open access
- green
- www.ncbi.nlm.nih.gov
- Licence
- Locations
- Angewandte Chemie International Edition (publishedVersion)
- PubMed (publishedVersion)
- Europe PMC (PubMed Central) (acceptedVersion)
- PubMed Central (acceptedVersion)
- Funders
- National Institutes of Health (R01GM111480, F32GM120823)
- Alfred P. Sloan Foundation
- National Science Foundation
- Topics
- Physical Sciences › Chemistry › Organic Chemistry › Catalytic Cross-Coupling Reactions
- Physical Sciences › Chemistry › Organic Chemistry › Organometallic Complex Synthesis and Catalysis
- Physical Sciences › Chemistry › Organic Chemistry › Inorganic and Organometallic Chemistry
- Keywords
- N-methyl-2-pyrrolidone, iron catalysis, cross-coupling, ferric salts, alkyl Grignard reagents, magnesium bromide, cosolvent effects, 57Fe Mössbauer spectroscopy, iron clusters, selective product formation
- MeSH terms
- Bromides, Catalysis, Ferric Compounds, Iron, Models, Molecular, Organometallic Compounds, Pyrrolidinones, Salts, Molecular Structure, Magnesium Compounds
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