Bioinspired functional iron model complexes related to nitrogenase will be generated focusing on the activation of dinitrogen. Key reduced nitrogen intermediates in a Chatt-type cycle will be isolated and the physical and spectroscopic properties of these compounds examined. The basic physical properties of iron nitrides, nitrenes, diazenidos, hydrazido, amido and amine functionalities are desired. Initially a series of strong field ligands will be examined. Low valent iron complexes of these ligands are capable of activating dinitrogen, but the subsequent reactivity has not been explored. Of particular interest are iron (IV)-nitrides for their applicability to group transfer processes. A number of spectroscopic studies will be undertaken to detail the electronic structures of these unique intermediates. The mechanism of formation and decay of metal-dinitrogen intermediates will be studied via kinetic and spectroscopic methods. In the next phase, sulfur rich ligands will be examined and the possibility of the application to group transfer processes will be examined. Through the principles of nitrogen activation gained from these biomimetic complexes, greater understanding of the role of iron in nitrogenase will be gained. ? ?

Agency
National Institute of Health (NIH)
Institute
National Institute of General Medical Sciences (NIGMS)
Type
Postdoctoral Individual National Research Service Award (F32)
Project #
1F32GM072291-01
Application #
6836615
Study Section
Special Emphasis Panel (ZRG1-F04A (20))
Program Officer
Lograsso, Philip
Project Start
2004-08-01
Project End
2006-07-31
Budget Start
2004-08-01
Budget End
2005-07-31
Support Year
1
Fiscal Year
2004
Total Cost
$41,068
Indirect Cost
Name
California Institute of Technology
Department
Chemistry
Type
Schools of Engineering
DUNS #
009584210
City
Pasadena
State
CA
Country
United States
Zip Code
91125
Iluc, Vlad M; Miller, Alexander J M; Anderson, John S et al. (2011) Synthesis and characterization of three-coordinate Ni(III)-imide complexes. J Am Chem Soc 133:13055-63
Mehn, Mark P; Peters, Jonas C (2006) Mid- to high-valent imido and nitrido complexes of iron. J Inorg Biochem 100:634-43
Hendrich, Michael P; Gunderson, William; Behan, Rachel K et al. (2006) On the feasibility of N2 fixation via a single-site FeI/FeIV cycle: Spectroscopic studies of FeI(N2)FeI, FeIV[triple bond]N, and related species. Proc Natl Acad Sci U S A 103:17107-12
Mehn, Mark P; Brown, Steven D; Jenkins, David M et al. (2006) Vibrational spectroscopy and analysis of pseudo-tetrahedral complexes with metal imido bonds. Inorg Chem 45:7417-27
Brown, Steven D; Mehn, Mark P; Peters, Jonas C (2005) Heterolytic H2 activation mediated by low-coordinate L3Fe-(mu-N)-FeL3 complexes to generate Fe(mu-NH)(mu-H)Fe species. J Am Chem Soc 127:13146-7