CHAPTER 8 - OXIDATION/PHOSPHORYLATION
E:
NITROGENASE - A REDUCTIVE USE OF METAL CENTERS
BIOCHEMISTRY - DR. JAKUBOWSKI
04/15/16
Learning Goals/Objectives for Chapter 8D:
- describe the structure, metal cofactors, and ligands of nitrogenase;
- describe the path of electrons from the mobile electron carrier to
the P cluster of nitrogenase;
- discuss the role of ATP in the nitrogenase reaction;
- draw and describe the Lowe and Thorneley cycle to show the
sequential additions of electrons and protons to nitrogenase;
- describe the properties of the E4 Janus intermediate and its role in
backward and forward reactions in the cycle;
- describe the role of H2 in the mechanism of nitrogenase;
- describe the organometallic reactions oxidative addition and
reductive elimination and their role in nitrogenase;
- explain the mechanisms and changes in oxidation states for Fe ions
and substrates/products for the first and second half of the nitrogenase
reaction.
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E6. Links and References
Brian M. Hoffman et al. Mechanism of Nitrogen
Fixation by Nitrogenase: The Next Stage, Chem. Rev. 2014, 114,
4041−4062 dx.doi.org/10.1021/cr400641x
Jared A. Wiig et al. Tracing the Interstitial
Carbide of the Nitrogenase Cofactor during Substrate Turnover. J Am
Chem Soc. 2013 April 3; 135(13): 4982–4983. doi:10.1021/ja401698d
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Chapter 8E: Nitrogenase -
A Reductive Use of Metal Centers
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