Characterization of Structurally Unusual Diiron N_xH_y Complexes
Abstract
Mechanistic proposals concerning the pathway of N_2 reduction in biology at the MoFe-cofactor of nitrogenase continue to be advanced. In addition to nitrogen, hydrazine2 and diazene1a are nitrogenase substrates, and recent DFT calculations and spectroscopic studies suggest that whereas initial N_2 binding may occur at one iron center, diiron pathways may be involved at certain N_xH_y intermediate stages en route to ammonia formation. In this broad context, recent work has explored the synthesis and spectroscopic characterization of structurally unusual mono- and bimetallic iron complexes featuring nitrogenous ligand functionalities. The demand for such model complexes continues in light of recent ENDOR and ESEEM spectroscopic data that has been obtained under turnover conditions at the cofactor. To date, there are few synthetic iron systems that feature parent hydrazine (N_2H_4), hydrazido (N_2H_2^(2-)), diazene (N_2H_2), amide (NH_(2)^-), and imide (NH^2-) ligands. Herein we describe the synthesis and characterization of a series of structurally distinct diiron complexes that feature each of these ligand types.
Additional Information
© 2009 American Chemical Society. Publication Date (Web): July 14, 2009. We acknowledge the NIH (GM-070757). Funding for the MIT Department of Chemistry Instrumentation Facility has been provided in part by the NSF (CHE-0234877). C.T.S. is grateful for an NSF graduate fellowship.Attached Files
Published - ja903967z_si_002.cif
Supplemental Material - ja903967z_si_001.pdf
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Additional details
- Alternative title
- Characterization of Structurally Unusual Diiron NxHy Complexes
- Eprint ID
- 52510
- Resolver ID
- CaltechAUTHORS:20141209-142810433
- NIH
- GM-070757
- NSF
- CHE-0234877
- Created
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2014-12-11Created from EPrint's datestamp field
- Updated
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2021-11-10Created from EPrint's last_modified field