Biochemistry Online: An Approach Based on Chemical Logic

Biochemistry Online

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.

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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