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Dinitrogen cleavage and functionalization by carbon monoxide promoted by a hafnium complex

Nature Chemistry volume 2, pages 30–35 (2010)Cite this article

Abstract

Molecular nitrogen (N2) and carbon monoxide (CO) have the two strongest bonds in chemistry and present significant challenges in developing new transformations that exploit these two abundant feedstocks. At the core of this objective is the discovery of transition-metal compounds that promote the six-electron reductive cleavage of N2 at ambient temperature and pressure and also promote new nitrogen–element bond formation. Here we show that an organometallic hafnium compound induces N2 cleavage on the addition of CO, with a simultaneous assembly of new nitrogen–carbon and carbon–carbon bonds. Subsequent addition of a weak acid liberates oxamide, which demonstrates that an important agrochemical can be synthesized directly from N2 and CO. These studies introduce an alternative paradigm for N2 cleavage and functionalization in which the six-electron reductive cleavage is promoted by both the transition metal and the incoming ligand, CO, used for the new bond formations.

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Figure 1: Synthesis and structure of the ansa-hafnocene N2 complex 2-N2.
Figure 2: Various N2 cleavage products from the addition of CO to a benzene-d6 solution of 2-N2.
Figure 3: NMR spectra of isotopologues of 2-(N2C2O2)-C1.
Figure 4: Solid-state structure of the (R,R) enantiomer of 2-(N2C2O2)-C2 at 30% probability ellipsoids.
Figure 5: Solid-state structure of 3 at 30% probability ellipsoids.
Figure 6: Proposed mechanism for the carbonylation of 2-N2 with one equivalent of CO to form 3.

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Acknowledgements

Financial support was provided by the Director, Office of Basic Energy Sciences, Chemical Sciences Division, of the US Department of Energy (DE-FG02-05ER15659) and the Frasch Foundation administered by the American Chemical Society.

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Authors and Affiliations

  1. Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, 14853, New York, USA

    Donald J. Knobloch, Emil Lobkovsky & Paul J. Chirik

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  1. Donald J. Knobloch
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Contributions

D.J.K. and P.J.C. conceived and designed the concepts and experiments. D.J.K. carried out the experiments, E.L. collected and solved the X-ray diffraction data and P.J.C. and D.J.K co-wrote the manuscript.

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Correspondence to Paul J. Chirik.

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The authors declare no competing financial interests.

Supplementary information

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Supplementary information (PDF 496 kb)

Supplementary information

Crystallographic data for compound 2-N2 (corrected 8 January 2010) (CIF 24 kb)

Supplementary information

Crystallographic data for compound 2-N2C2O2 (CIF 26 kb)

Supplementary information

Crystallographic data for compound 3 (CIF 24 kb)

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Knobloch, D., Lobkovsky, E. & Chirik, P. Dinitrogen cleavage and functionalization by carbon monoxide promoted by a hafnium complex. Nature Chem 2, 30–35 (2010). https://doi.org/10.1038/nchem.477

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