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A molybdenum complex bearing PNP-type pincer ligands leads to the catalytic reduction of dinitrogen into ammonia

Nature Chemistry volume 3, pages 120–125 (2011)Cite this article

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Abstract

The synthesis of transition metal–dinitrogen complexes and the stoichiometric transformation of their coordinated dinitrogen into ammonia and hydrazine have been the subject of considerable research, with a view to achieving nitrogen fixation under ambient conditions. Since a single example in 2003, no examples have been reported of the catalytic conversion of dinitrogen into ammonia under ambient conditions. The dimolybdenum–dinitrogen complex bearing PNP pincer ligands was found to work as an effective catalyst for the formation of ammonia from dinitrogen, with 23 equiv. of ammonia being produced with the catalyst (12 equiv. of ammonia are produced based on the molybdenum atom of the catalyst). This is another successful example of the catalytic and direct conversion of dinitrogen into ammonia under ambient reaction conditions. We believe that the results described in this Article provide valuable information with which to develop a more effective nitrogen-fixation system under mild reaction conditions.

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Figure 1: Preparation and molecular structure of dinitrogen-bridged dimolybdenum complex 2a.
Figure 2: Catalytic conversion of dinitrogen into ammonia in the presence of 2a as a catalyst.
Figure 3: Reaction pathway for catalytic conversion of dinitrogen into ammonia in the presence of 2a as catalyst.

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Acknowledgements

The authors are grateful to Y.K. Kato and T. Shimada (University of Tokyo) for Raman spectroscopy measurements and to K. Nozaki and K. Nakano (University of Tokyo) for TOF MS analysis. This work was supported by Grant-in-Aids for Scientific Research for Young Scientists (S) (no. 19675002) and for Scientific Research on Priority Areas (no. 18066003) from the Ministry of Education, Culture, Sports, Science and Technology, Japan.

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Authors and Affiliations

  1. Institute of Engineering Innovation, School of Engineering, The University of Tokyo, Yayoi, Bunkyo-ku, 113-8656, Tokyo, Japan

    Kazuya Arashiba, Yoshihiro Miyake & Yoshiaki Nishibayashi

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  1. Kazuya Arashiba
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  2. Yoshihiro Miyake
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  3. Yoshiaki Nishibayashi
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Contributions

Y.N. directed and conceived the project and wrote the manuscript. K.A. designed and performed all experiments, including the X-ray study, and wrote the experimental details in the Supplementary Information. Y.M. carried out Raman spectroscopy measurements and TOF MS analysis. All authors discussed the results and commented on the paper.

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Correspondence to Yoshiaki Nishibayashi.

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The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 983 kb)

Supplementary information

Crystallographic data for compound 1a (CIF 63 kb)

Supplementary information

Crystallographic data for compound 2a (CIF 31 kb)

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Crystallographic data for compound 3a (CIF 40 kb)

Supplementary information

Crystallographic data for compound 7a (CIF 43 kb)

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Arashiba, K., Miyake, Y. & Nishibayashi, Y. A molybdenum complex bearing PNP-type pincer ligands leads to the catalytic reduction of dinitrogen into ammonia. Nature Chem 3, 120–125 (2011). https://doi.org/10.1038/nchem.906

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