Triggering N_2 uptake via redox-induced expulsion of coordinated NH_3 and N_2 silylation at trigonal bipyramidal iron
- Creators
- Lee, Yunho
- Mankad, Neal P.
-
Peters, Jonas C.
Abstract
The biological reduction of N_2 to give NH_3 may occur by one of two predominant pathways in which nitrogenous N_xH_y intermediates, including hydrazine (N_2H_4), diazene (N_2H_2), nitride (N^(3-)) and imide (NH^(2-)), may be involved. To test the validity of hypotheses on iron's direct role in the stepwise reduction of N_2, model systems for iron are needed. Such systems can test the chemical compatibility of iron with various proposed N_xH_y intermediates and the reactivity patterns of such species. Here we describe a trigonal bipyramidal Si(o-C_6H_4PR_2)_3Fe–L scaffold (R=Ph or i-Pr) in which the apical site is occupied by nitrogenous ligands such as N_2, N_2H_4, NH_3 and N_2R. The system accommodates terminally bound N_2 in the three formal oxidation states (iron(0), +1 and +2). N_2 uptake is demonstrated by the displacement of its reduction partners NH_3 and N_2H_4, and N_2 functionalizaton is illustrated by electrophilic silylation.
Additional Information
© 2010 Macmillan Publishers Limited. Received 23 November 2009. Accepted 29 March 2010. Published online 16 May 2010. We acknowledge the National Institutes of Health (GM-070757). Funding for the Massechussetts Institute of Technology Department of Chemistry Instrumentation Facility was provided in part by the National Science Foundation (NSF) (CHE-0234877). P. Mueller provided assistance with XRD analyses. N.P.M. received an NSF graduate fellowship. We thank R.H. Holm and T.A. Betley at Harvard University for providing us with access to a Mössbauer spectrometer. Author contributions: Y.L., N.P.M. and J.C.P. conceived and designed the experiments, Y.L. and N.P.M. performed the experiments and Y.L. and J.C.P. co-wrote the paper.Attached Files
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Additional details
- Eprint ID
- 19353
- DOI
- 10.1038/NCHEM.660
- Resolver ID
- CaltechAUTHORS:20100810-073448823
- NIH
- GM-070757
- NSF
- CHE-0234877
- Created
-
2010-08-10Created from EPrint's datestamp field
- Updated
-
2021-11-08Created from EPrint's last_modified field