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Published October 23, 2009 | Accepted Version + Supplemental Material
Journal Article Open

Carbenes As Catalysts for Transformations of Organometallic Iron Complexes


Compared with the enormous arsenal of catalysts used to produce organic compounds, complementary species that are able to mediate sophisticated organometallic transformations are virtually nonexistent. We found that stable N-heterocyclic carbenes (NHCs) can mediate unusual organometallic transformations in solution at room temperature. Depending on the choice of NHC initiator, stoichiometric or catalytic reactions of bis(cyclooctatetraene)iron [Fe(COT)_2] ensue. The stoichiometric reaction leads to the isolation of a previously unknown mixed-valent species, featuring distinct and directly bonded Fe(0) and Fe(I) centers. In the catalytic process, three iron atoms are fused to afford the tri-iron cluster Fe_3(COT)_3, which is a hydrocarbon analog of Dewar's classic Fe_3(CO)_(12) complex. The key step in both of these processes is proposed to involve the NHC's ability to induce metal–metal bond formation. These NHC-mediated reactions provide a foundation on which to develop future organometallic transformations that are catalyzed by organic species.

Additional Information

© 2009 American Association for the Advancement of Science. 10 July 2009; accepted 13 August 2009. We gratefully acknowledge financial support from NIH for grant 5RO1 GM31332 and a National Research Service Award Postdoctoral Fellowship (to V.L.). We thank L. M. Henling and M. W. Day (California Institute of Technology) for x-ray crystallographic analysis. The Bruker KAPPA APEX II x-ray diffractometer was purchased via an NSF Chemistry Research Instrumentation and Facilities: Multi-User award to the California Institute of Technology, CHE-0639094. Crystallographic data for complexes 3 and 8 are available free of charge from the Cambridge Crystallographic Data Center under reference numbers CCDC-724011 and CCDC-728138, respectively.

Attached Files

Accepted Version - nihms184788.pdf

Supplemental Material - Lavallo.SOM.pdf


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