Review

Half-Sandwich Iron Complexes: From Organometallic Reactivity to Catalyst Design

Received: 14 August 2026; Revised: 31 August 2026; Accepted: 2 September 2026; Published: 3 September 2026
DOI: https://doi.org/10.54963/ssi.103379
Preview PDF

Abstract

Half-sandwich iron complexes have long provided a versatile platform for organometallic chemistry, yet their potential as earth-abundant catalysts with deliberately engineered reactivity is only beginning to emerge. This review examines how the reactivity of the half-sandwich framework has evolved from classical stoichiometric iron chemistry towards catalytic systems in which ligand design and ligand cooperativity play increasingly active roles. Selected studies illustrate how the iron center can encode stereochemical information, how ligand frameworks can participate directly in substrate activation and how ligand structure can redirect competing reaction pathways. These examples highlight the modularity of half-sandwich iron complexes as a platform for earth-abundant iron catalysis design and suggest broader opportunities to control their reactivity through deliberate modification of the metal–ligand environment.

Graphical Abstract

Figure

References

  1. Fürstner, A. Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion. ACS Cent. Sci. 2016, 2 (11), 778–789. https://doi.org/10.1021/acscentsci.6b00272.
  2. Bullock, R. M.; Chen, J. G.; Gagliardi, L.; Chirik, P. J.; Farha, O. K.; Hendon, C. H.; Jones, C. W.; Keith, J. A.; Klosin, J.; Minteer, S. D.; Morris, R. H.; Radosevich, A. T.; Rauchfuss, T. B.; Strotman, N. A.; Vojvodic, A.; Ward, T. R.; Yang, J. Y.; Surendranath, Y. Using Nature’s Blueprint to Expand Catalysis with Earth-Abundant Metals. Science 2020, 369 (6505), eabc3183. https://doi.org/10.1126/science.abc3183.
  3. Bauer, I.; Knölker, H.-J. Iron Catalysis in Organic Synthesis. Chem. Rev. 2015, 115 (9), 3170–3387. https://doi.org/10.1021/cr500425u.
  4. Shang, R.; Ilies, L.; Nakamura, E. Iron-Catalyzed C–H Bond Activation. Chem. Rev. 2017, 117 (13), 9086–9139. https://doi.org/10.1021/acs.chemrev.6b00772.
  5. Kelly, W. J. Bis(Dicarbonylcyclopentadienyliron). In Encyclopedia of Reagents for Organic Synthesis; John Wiley & Sons, Ltd, 2001. https://doi.org/10.1002/047084289X.rb139.
  6. Korb, M. Iron Half-Sandwich Complexes for Catalysis. In Encyclopedia of Inorganic and Bioinorganic Chemistry; John Wiley & Sons, Ltd, 2022; pp 1–37. https://doi.org/10.1002/9781119951438.eibc2786.
  7. Helquist, P. Development of Carbene Complexes of Iron as New Reagents for Synthetic Organic Chemistry. In Advances in Metal-Organic Chemistry; Elsevier, 1991; Vol. 2, pp 143–194. https://doi.org/10.1016/B978-0-89232-948-9.50008-3.
  8. Brookhart, Maurice.; Studabaker, W. B. Cyclopropanes from Reactions of Transition Metal Carbene Complexes with Olefins. Chem. Rev. 1987, 87 (2), 411–432. https://doi.org/10.1021/cr00078a008.
  9. Wang, Y.; Zhu, J.; Durham, A. C.; Lindberg, H.; Wang, Y.-M. α-C–H Functionalization of π-Bonds Using Iron Complexes: Catalytic Hydroxyalkylation of Alkynes and Alkenes. J. Am. Chem. Soc. 2019, 141 (50), 19594–19599. https://doi.org/10.1021/jacs.9b11716.
  10. Liang, Q.; Osten, K. M.; Song, D. Iron-Catalyzed Gem-Specific Dimerization of Terminal Alkynes. Angewandte Chemie International Edition 2017, 56 (22), 6317–6320. https://doi.org/10.1002/anie.201700904.
  11. Liu, J.; Song, H.; Wang, T.; Jia, J.; Tong, Q.-X.; Tung, C.-H.; Wang, W. Iron-Catalyzed Regiodivergent Hydrostannation of Alkynes: Intermediacy of Fe(IV)–H versus Fe(II)–Vinylidene. J. Am. Chem. Soc. 2021, 143 (1), 409–419. https://doi.org/10.1021/jacs.0c11448.
  12. Brookhart, M.; Nelson, G. O. Isolation of Stable Secondary Cationic Iron Carbene Complexes Dicarbonyl(.Eta.5-Cyclopentadienyl)Phenylcarbeneiron Hexafluorophosphate and Carbonyl(.Eta.5-Cyclopentadienyl)Triphenylphosphine(Phenylcarbene)Iron Hexafluorophosphate. J. Am. Chem. Soc. 1977, 99 (18), 6099–6101. https://doi.org/10.1021/ja00460a045.
  13. Adams, H.; Bailey, N. A.; Ridgway, C.; Taylor, B. F.; Walters, S. J.; Winter, M. J. Carbene Formation from CpM(SnPh3)(CO)2(M = Fe, Ru). Crystal Structures of CpFeI(CO){=C(OEt)Ph}, CpRuI(CO){=C(OEt)Ph} and CpRuI(CO){=C(NHMe)Ph}. J. Organometal. Chem. 1990, 394 (1), 349–364. https://doi.org/10.1016/0022-328X(90)87244-8.
  14. Brandt, S.; Helquist, P. Cyclopropanation of Olefins with a Stable, Iron-Containing Methylene Transfer Reagent. J. Am. Chem. Soc. 1979, 101 (21), 6473–6475. https://doi.org/10.1021/ja00515a074.
  15. Helquist, P. Dicarbonyl(Cyclopentadienyl)[(Dimethylsulfonium)Methyl]Iron Tetrafluoroborate. In Encyclopedia of Reagents for Organic Synthesis; John Wiley & Sons, Ltd, 2001. https://doi.org/10.1002/047084289X.rd079.
  16. Beutner, G. L.; George, D. T. Opportunities for the Application and Advancement of the Corey–Chaykovsky Cyclopropanation. Org. Process Res. Dev. 2022, 27 (1), 10–41. https://doi.org/10.1021/acs.oprd.2c00315.
  17. Knors, C.; Kuo, G. H.; Lauher, J. W.; Eigenbrot, C.; Helquist, P. Preparation, Structure, and Reactions of Stable Mono(Alkylthio)Carbene Iron Complexes of the (.Eta.5-C5H5)(CO)2Fe System. Organometallics 1987, 6 (5), 988–995. https://doi.org/10.1021/om00148a017.
  18. Zhao, S. K.; Knors, C.; Helquist, P. Intramolecular Carbon-Hydrogen Insertion Reactions of (Cyclopentadienyl)Dicarbonyl Iron Carbene Complexes. J. Am. Chem. Soc. 1989, 111 (22), 8527–8528. https://doi.org/10.1021/ja00204a040.
  19. Ishii, S.; Helquist, P. Intramolecular C-H Insertion Reactions of Iron Carbene Complexes as a General Method for Synthesis of Bicyclo[n.3.0]Alkanones. Synlett 1997, 4, 508–510. https://doi.org/10.1055/s-1997-6122.
  20. Ishii, S.; Zhao, S.; Helquist, P. Stereochemical Probes of Intramolecular C−H Insertion Reactions of Iron-Carbene Complexes. J. Am. Chem. Soc. 2000, 122 (24), 5897–5898. https://doi.org/10.1021/ja000239f.
  21. Ishii, S.; Zhao, S.; Mehta, G.; Knors, C. J.; Helquist, P. Intramolecular C−H Insertion Reactions of (η⁵-Cyclopentadienyl)dicarbonyliron Carbene Complexes:  Scope of the Reactions and Application to the Synthesis of (±)-Sterpurene and (±)-Pentalenene. J. Org. Chem. 2001, 66 (10), 3449–3458. https://doi.org/10.1021/jo001792i.
  22. Brookhart, M.; Timmers, D.; Tucker, J. R.; Williams, G. D.; Husk, G. R.; Brunner, H.; Hammer, B. Enantioselective Cyclopropane Synthesis Using the Chiral Carbene Complexes (SFeSC)- and (RFeSC)-(C5H5)(CO)(Ph2R*P)Fe:CHCH3+ (R* = (S)-2-Methylbutyl). Role of Metal vs. Ligand Chirality in the Optical Induction. J. Am. Chem. Soc. 1983, 105 (22), 6721–6723. https://doi.org/10.1021/ja00360a034.
  23. Brookhart, M.; Liu, Y.; Goldman, E. W.; Timmers, D. A.; Williams, G. D. Enantioselective Cyclopropane Syntheses Using the Chiral Carbene Complexes (SFe)- and (RFe)-C5H5(CO)(PR3)Fe:CHCH3+. A Mechanistic Analysis of the Carbene Transfer Reaction. J. Am. Chem. Soc. 1991, 113 (3), 927–939. https://doi.org/10.1021/ja00003a028.
  24. Cutler, A.; Ehnholt, D.; Lennon, P.; Nicholas, K.; Marten, D. F.; Madhavarao, M.; Raghu, S.; Rosan, A.; Rosenblum, M. Chemistry of Dicarbonyl .Eta.5-Cyclopentadienyliron Complexes. General Syntheses of Monosubstituted .Eta.2-Olefin Complexes and of 1-Substituted .Eta.1-Allyl Complexes. Conformational Effects on the Course of Deprotonation of (.Eta.2-Olefin) Cations. J. Am. Chem. Soc. 1975, 97 (11), 3149–3157. https://doi.org/10.1021/ja00844a038.
  25. Rosenblum, M. Organoiron Complexes as Potential Reagents in Organic Synthesis. Acc. Chem. Res. 1974, 7 (4), 122–128. https://doi.org/10.1021/ar50076a004.
  26. Jiang, S.; Agoston, G. E.; Chen, T.; Cabal, M.-P.; Turos, E. BF3.Cntdot.Et2O-Promoted Allylation Reactions of Allyl(Cyclopentadienyl)Iron(II) Dicarbonyl Complexes with Carbonyl Compounds. Organometallics 1995, 14 (10), 4697–4709. https://doi.org/10.1021/om00010a037.
  27. Wang, R.; Wang, Y.; Ding, R.; Staub, P. B.; Zhao, C. Z.; Liu, P.; Wang, Y.-M. Designed Iron Catalysts for Allylic C−H Functionalization of Propylene and Simple Olefins. Angew. Chem. Int. Ed. 2023, 62 (10), e202216309. https://doi.org/10.1002/anie.202216309.
  28. Scrivener, S. G.; Wang, Y.-M. A C–H Functionalization Approach to Diverse Nitrogenous Scaffolds through Conjugate Addition of Catalytic Allyliron Nucleophiles. Chem. Sci. 2024, 15 (23), 8850–8857. https://doi.org/10.1039/D4SC00655K.
  29. Wang, Y.; Scrivener, S. G.; Zuo, X.-D.; Wang, R.; Palermo, P. N.; Murphy, E.; Durham, A. C.; Wang, Y.-M. Iron-Catalyzed Contrasteric Functionalization of Allenic C(Sp2)–H Bonds: Synthesis of α‑Aminoalkyl 1,1-Disubstituted Allenes. J. Am. Chem. Soc. 2021, 143 (37), 14998–15004. https://doi.org/10.1021/jacs.1c07512.
  30. Ding, R.; Wang, Y.; Wang, Y.-M. Synthesis of 1,1-Disubstituted Allenylic Silyl Ethers through Iron-Catalyzed Regioselective C(Sp2)–H Functionalization of Allenes. Synthesis 2023, 55 (05), 733–743. https://doi.org/10.1055/a-2004-0951.
  31. Scrivener, S. G.; Wang, Y.; Wang, Y.-M. Iron-Catalyzed Coupling of Alkenes and Enones: Sakurai–Michael-Type Conjugate Addition of Catalytic Allyliron Nucleophiles. Org. Lett. 2023, 25 (9), 1420–1424. https://doi.org/10.1021/acs.orglett.3c00139.
  32. Durham, A. C.; Liu, C. R.; Wang, Y.-M. Iron-Mediated C−H Functionalization of Unactivated Alkynes for the Synthesis of Derivatized Dihydropyrrolones: Regioselectivity Under Thermodynamic Control. Chem. Eur. J. 2023, 29 (45), e202301195. https://doi.org/10.1002/chem.202301195.
  33. Dey, S.; Charlack, A. D.; Durham, A. C.; Zhu, J.; Wang, Y.; Wang, Y.-M. Synthesis of 1,3-Enynes by Iron-Catalyzed Propargylic C–H Functionalization: An Alkyne Analogue for the Eschenmoser Methenylation. Org. Lett. 2024, 26 (16), 3355–3360. https://doi.org/10.1021/acs.orglett.4c00696.
  34. Xia, Y.; Zhu, J.; Durham, A. C.; Wang, Y.-M. An Organometallic Umpolung Approach for Iron-Mediated Propargylic C−H Etherification. Angew, Chem, Int. Ed. 2024, 136 (52), e202413017. https://doi.org/10.1002/anie.202413017.
  35. Liang, Q.; Hayashi, K.; Song, D. Catalytic Alkyne Dimerization without Noble Metals. ACS Catal. 2020, 10 (9), 4895–4905. https://doi.org/10.1021/acscatal.0c00988.
  36. Liang, Q.; Sheng, K.; Salmon, A.; Zhou, V. Y.; Song, D. Active Iron(II) Catalysts toward Gem -Specific Dimerization of Terminal Alkynes. ACS Catal. 2019, 9 (2), 810–818. https://doi.org/10.1021/acscatal.8b03552.
  37. Liang, Q.; Hayashi, K.; Rabeda, K.; Jimenez-Santiago, J. L.; Song, D. Piano-Stool Iron Complexes as Precatalysts for Gem -Specific Dimerization of Terminal Alkynes. Organometallics 2020, 39 (12), 2320–2326. https://doi.org/10.1021/acs.organomet.0c00271.
  38. Liang, Q.; Song, D. Syntheses and Reactivity of Piano-Stool Iron Complexes of Picolyl-Functionalized N-Heterocyclic Carbene Ligands. Organometallics 2021, 40 (23), 3943–3951. https://doi.org/10.1021/acs.organomet.1c00515.
  39. Liang, Q.; Garcia Mayerstein, H. A.; Song, D. Reactivity of a Piano-Stool Iron Complex toward Boranes. Organometallics 2023, 42 (9), 816–824. https://doi.org/10.1021/acs.organomet.3c00037.
  40. Li, Y.; Chen, J.-Y.; Miao, Q.; Yu, X.; Feng, L.; Liao, R.-Z.; Ye, S.; Tung, C.-H.; Wang, W. A Parent Iron Amido Complex in Catalysis of Ammonia Oxidation. J. Am. Chem. Soc. 2022, 144 (10), 4365–4375. https://doi.org/10.1021/jacs.1c08609.
  41. Gao, H.; Jia, J.; Tung, C.-H.; Wang, W. Iron-Catalyzed Selective Hydroboration of CO2 by Cooperative B–H Bond Activation. Organometallics 2023, 42 (10), 944–951. https://doi.org/10.1021/acs.organomet.3c00119.
  42. Zhao, Q.; Li, C.; Gao, H.; Cao, Y.-C.; Liao, R.-Z.; Wang, W. Iron-Catalyzed Regioselective C═C Bond Migration and Reductive Deuteration. J. Org. Chem. 2025, 90 (18), 6304–6312. https://doi.org/10.1021/acs.joc.5c00449.