Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Nitrogen reduction

Molybdenum does it again

Nature Chemistry volume 3, pages 95–96 (2011)Cite this article

Subjects

Nature reduces dinitrogen under mild conditions using nitrogenases, the most active of which contains molybdenum and iron. The only abiological dinitrogen reduction catalyst that avoids the harsh conditions of the Haber–Bosch process contains just molybdenum.

Ammonia is necessary for all life, because it is the source of nitrogen in essential biomolecules such as proteins and DNA. More than 108 tons per year of ammonia are formed in the environment through reduction of molecular nitrogen in the air by nitrogenase enzymes1,2. A roughly equal amount is formed in the Haber–Bosch process (at 350–550 °C and 150–350 atm) through reduction of purified nitrogen with hydrogen3; a process that is arguably the most important industrial process discovered in the twentieth century and partially responsible — by enabling the production of nitrogen-based fertilizers — for a doubling of the population of the earth. It would nevertheless be desirable to reduce molecular nitrogen in a man-made process under milder conditions, because the energy-intensive process demands around 1.5% of the world's annual energy supply. Discovering such a process would also help us understand how the remarkable and complex catalytic reduction of molecular nitrogen is achieved in naturally occurring nitrogenases. Only one catalytic reduction of molecular nitrogen directly to ammonia is known; the reduction is catalysed by a [HIPTN3N]Mo(III) catalyst, where [HIPTN3N]3− = {[3,5-(2,4,6-iPr3C6H2)2C6H3NCH2CH2]3N}3− (ref. 4). The only other abiological catalytic reduction of dinitrogen under mild conditions also employs molybdenum, but yields hydrazine as a primary product, which is then disproportionated into nitrogen and ammonia5.

This is a preview of subscription content

Access options

Buy article

Get time limited or full article access on ReadCube.

$32.00

Buy

All prices are NET prices.

Figure 1: Dinitrogen is reduced catalytically, by employing lutidinium triflate as the proton source and cobaltocene as the electron source, in toluene at room temperature.

References

  1. Burgess, B. K. & Lowe, D. J. Chem. Rev. 96, 2983–3011 (1996).

    CAS  Article  Google Scholar 

  2. Eady, R. R. Chem. Rev. 96, 3013–3030 (1996).

    CAS  Article  Google Scholar 

  3. Smil, V. Enriching The Earth: Fritz Haber, Carl Bosch, and the Transformation of World Food Production (MIT Press, 2004).

    Google Scholar 

  4. Schrock, R. R. Angew. Chem. Int. Ed. 47, 5512–5522 (2008).

    CAS  Article  Google Scholar 

  5. Shilov, A. E. Russ. Chem. Bull. Int. Ed. 52, 2555–2562 (2003).

    CAS  Article  Google Scholar 

  6. Arashiba, K., Miyake, Y. & Nishibayashi, Y. Nature Chem. 3, 120–125 10.1038/nchem.906 (2011).

    CAS  Article  Google Scholar 

  7. Chatt, J., Dilworth, J. R. & Richards, R. L. Chem. Rev. 78, 589–625 (1978).

    CAS  Article  Google Scholar 

  8. Hidai, M. Coord. Chem. Rev. 185–186, 99–108 (1999).

    Article  Google Scholar 

  9. Barriere, F. Coord. Chem. Rev. 236, 71–89 (2003).

    CAS  Article  Google Scholar 

  10. MacKay, B. A. & Fryzuk, M. D. Chem. Rev. 104, 385–401 (2004).

    CAS  Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Richard R. Schrock is in the Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachussetts 02139, USA. rrs@mit.edu,

    Richard R. Schrock

Authors
  1. Richard R. Schrock
    View author publications

    You can also search for this author in PubMed Google Scholar

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Schrock, R. Molybdenum does it again. Nature Chem 3, 95–96 (2011). https://doi.org/10.1038/nchem.977

Download citation

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nchem.977

Further reading

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing