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

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.

References

  1. 1

    Ertl, G. Reactions at surfaces: from atoms to complexity (Nobel Lecture). Angew. Chem. Int. Ed. 47, 3524–3535 (2008).

    CAS  Article  Google Scholar 

  2. 2

    Smil, V. Enriching the Earth: Fritz Haber, Carl Bosch, and the Transformation of World Food Production (MIT Press, 2001).

    Google Scholar 

  3. 3

    Holladay, J. D., Hu, J., King, D. L. & Wang, Y. An overview of hydrogen production technologies. Catal. Today 139, 244–260 (2009).

    CAS  Article  Google Scholar 

  4. 4

    Thomas, J. M. & Thomas, W. J. Fischer–Tropsch Catalysis, in Principles and Practice of Heterogeneous Catalysis (VCH, 1996).

  5. 5

    Macho, V., Kralik, M. & Komora, L. Progress in commercial and potential industrial processes based on carbon monoxide. Petrol. Coal 39, 6–12 (1997).

    CAS  Google Scholar 

  6. 6

    MacLachlan, E. A. & Fryzuk, M. D. Synthesis and reactivity of side-on-bound dinitrogen metal complexes. Organometallics 25, 1530–1543 (2006).

    CAS  Article  Google Scholar 

  7. 7

    Pool, J. A., Lobkovsky, E. & Chirik, P. J. Hydrogenation and cleavage of dinitrogen to ammonia with a zirconium complex. Nature 427, 527–530 (2004).

    CAS  Article  PubMed  PubMed Central  Google Scholar 

  8. 8

    Fryzuk, M. D., Love, J. B. & Rettig, S. J. Transformation of coordinated dinitrogen by reaction with dihydrogen and primary silanes. Science 275, 1445–1447 (1997).

    CAS  Article  Google Scholar 

  9. 9

    Pun, D., Bradley, C. A., Lobkovsky, E., Keresztes, I. & Chirik, P. J. N2 hydrogenation from activated end-on bis(indenyl) zirconium dinitrogen complexes. J. Am. Chem. Soc. 130, 14046–14047 (2008).

    CAS  Article  PubMed  PubMed Central  Google Scholar 

  10. 10

    Bernskoetter, W. H., Lobkovsky, E. & Chirik, P. J. Kinetics and mechanism of N2 hydrogenation in bis(cyclopentadienyl) zirconium complexes and dinitrogen functionalization by 1,2-addition of a saturated C–H bond. J. Am. Chem. Soc. 127, 14051–14061 (2005).

    CAS  Article  PubMed  PubMed Central  Google Scholar 

  11. 11

    Bernskoetter, W. H., Pool, J. A., Lobkovsky, E. & Chirik, P. J. Dinitrogen functionalization with terminal alkynes, amines, and hydrazines promoted by [(η5-C5Me4H)2Zr]2(μ2,η22-N2): observation of side-on and end-on diazenido complexes in the reduction of N2 to hydrazine. J. Am. Chem. Soc. 127, 7901–7911 (2005).

    CAS  Article  PubMed  PubMed Central  Google Scholar 

  12. 12

    Bernskoetter, W. H., Olmos, A. V., Lobkovsky, E. & Chirik, P. J. N2 hydrogenation promoted by a side-on bound hafnocene dinitrogen complex. Organometallics 25, 1021–1027 (2006).

    CAS  Article  Google Scholar 

  13. 13

    Morello, L., Love, J. B., Patrick, B. O. & Fryzuk, M. D. Carbon–nitrogen bond formation via the reaction of terminal alkynes with a dinuclear side-on dinitrogen complex. J. Am. Chem. Soc. 126, 9480–9481 (2004).

    CAS  Article  PubMed  PubMed Central  Google Scholar 

  14. 14

    Bernskoetter, W. H., Olmos, A. V., Pool, J. A., Lobkovsky, E. & Chirik, P. J. N–C bond formation promoted by a hafnocene dinitrogen complex: comparison of zirconium and hafnium congeners. J. Am. Chem. Soc. 128, 10696–10697 (2006).

    CAS  Article  PubMed  PubMed Central  Google Scholar 

  15. 15

    Bernskoetter, W. H., Lobkovsky, E. & Chirik, P. J. Nitrogen–carbon bond formation from N2 and CO2 promoted by a hafnocene dinitrogen complex yields a substituted hydrazine. Angew. Chem. Int. Ed. 46, 2858–2861 (2007).

    CAS  Article  Google Scholar 

  16. 16

    Knobloch, D. J., Toomey, H. E. & Chirik, P. J. Carboxylation of an ansa-zirconocene dinitrogen complex: regiospecific hydrazine synthesis from N2 and CO2 . J. Am. Chem. Soc. 130, 4248–4249 (2008).

    CAS  Article  PubMed  PubMed Central  Google Scholar 

  17. 17

    Hanna, T. E., Keresztes, I., Lobkovsky, E. & Chirik, P. J. Diazene dehydrogenation follows H2 addition to coordinated dinitrogen in an ansa-zirconocene complex. Inorg. Chem. 46, 1675–1683 (2007).

    CAS  Article  PubMed  PubMed Central  Google Scholar 

  18. 18

    Hirotsu, M., Fontaine, P. P., Zavalij, P. Y. & Sita, L. R. Extreme N≡N bond elongation and facile N-atom functionalization reactions within two structurally versatile new families of group 4 bimetallic ‘side-on-bridged’ dinitrogen complexes for zirconium and hafnium. J. Am. Chem. Soc. 129, 12690–12692 (2007).

    CAS  Article  PubMed  PubMed Central  Google Scholar 

  19. 19

    Roesky, H., Amin, N., Remmers, G., Gieren, A. & Dederer, B. Formal criss-cross cycloaddition of sulfur trioxide to cyanogen. Angew. Chem. Int. Ed. Engl. 18, 223 (1979).

    Article  Google Scholar 

  20. 20

    Laplaza, C. E. & Cummins, C. C. Dinitrogen cleavage by a three-coordinate molybdenum(iii) complex. Science 268, 861–863 (1995).

    CAS  Article  PubMed  PubMed Central  Google Scholar 

  21. 21

    Laplaza, C. E. et al. Dinitrogen cleavage by three-coordinate molybdenum(iii) complexes: mechanistic and structural data. J. Am. Chem. Soc. 118, 8623–8638 (1996).

    CAS  Article  Google Scholar 

  22. 22

    Curley, J. J., Cook, T. R., Reece, S. Y., Müller, P. & Cummins, C. C. Shining light on dinitrogen cleavage: structural features, redox chemistry, and photochemistry of the key intermediate bridging dinitrogen complex. J. Am. Chem. Soc. 130, 9394–9405 (2008).

    CAS  Article  PubMed  PubMed Central  Google Scholar 

  23. 23

    McKay, B. A. & Fryzuk, M. D. Dinitrogen coordination chemistry: on the biomimetic borderlands. Chem. Rev. 104, 385–401 (2004).

    Article  Google Scholar 

  24. 24

    Fryzuk, M. D. Side-on end-on bound dinitrogen: an activated bonding mode that facilitates functionalizing molecular nitrogen. Acc. Chem. Res. 42, 127–133 (2009).

    CAS  Article  PubMed  PubMed Central  Google Scholar 

  25. 25

    Curley, J. J., Sceats, E. L. & Cummins, C. C. A cycle for organic nitrile synthesis via dinitrogen cleavage. J. Am. Chem. Soc. 128, 14036–14037 (2006).

    CAS  Article  PubMed  PubMed Central  Google Scholar 

  26. 26

    Akagi, F., Matsuo, T. & Kawaguchi, H. Dinitrogen cleavage by a diniobium tetrahydride complex: formation of a nitride and its conversion into imide species. Angew. Chem. Int. Ed. 46, 8778–8781 (2007).

    CAS  Article  Google Scholar 

  27. 27

    Chatt, J., Pearman, A. J. & Richards, R. L. Conversion of dinitrogen in its molybdenum and tungsten complexes into ammonia and possible relevance to nitrogenase reaction. J. Chem. Soc. Dalton Trans. 1852–1860 (1977).

  28. 28

    Yandulov, D. V. & Schrock, R. R. Catalytic reduction of dinitrogen to ammonia at a single molybdenum center. Science 301, 76–78 (2003).

    CAS  Article  PubMed  Google Scholar 

  29. 29

    Schrock, R. R. Catalytic reduction of dinitrogen to ammonia at a single molybdenum center. Acc. Chem. Res. 38, 955–962 (2005).

    CAS  Article  PubMed  PubMed Central  Google Scholar 

  30. 30

    Mori, M. Synthesis of nitrogen heterocycles utilizing molecular nitrogen as a nitrogen source and attempt to use air instead of nitrogen gas. Heterocycles 78, 281–318 (2009).

    CAS  Article  Google Scholar 

  31. 31

    Nikiforov, G. B., Vidyaratne, I., Gambarotta, S. & Korobkov, I. Titanium-promoted dinitrogen cleavage, partial hydrogenation, and silylation. Angew. Chem. Int. Ed. 48, 7415–7419 (2009).

    CAS  Article  Google Scholar 

  32. 32

    Watanabe, T., Ishida, Y., Matsuo, T. & Kawaguchi, H. Reductive coupling of six carbon monoxides by a ditantalum hydride complex. J. Am. Chem. Soc. 131, 3474–3475.

  33. 33

    Summerscales, O. T., Cloke, F. G. N., Hitchcock, P. B., Green, J. C. & Hazari, N. Reductive cyclotrimerization of carbon monoxide to the deltate dianion by an organometallic uranium complex. Science 311, 829–831 (2006).

    CAS  Article  PubMed  PubMed Central  Google Scholar 

  34. 34

    Herrmann, H., Fillol, J. L., Wadepohl, H. & Gade, L. H. A zirconium (1-pyridinio)imido complex: facile N–N bond cleavage and N–C bond formation. Organometallics 27, 172–174 (2008).

    CAS  Article  Google Scholar 

  35. 35

    Herrmann, H., Fillol, J. L., Wadepohl, H. & Gade, L. H. A zirconium hydrazide as a synthon for a metallanitrene equivalent: atom-by-atom assembly of [EN2]2− units (E = S, Se) by chalcogen-atom transfer in the coordination sphere of a transition metal. Angew. Chem. Int. Ed. 46, 8426–8430 (2007).

    CAS  Article  Google Scholar 

  36. 36

    Selby, J. D. et al. New ligand platforms for developing the chemistry of the Ti=N–NR2 functional group and the insertion of alkynes into the N–N bond of a Ti=N–NPh2 ligand. Chem. Commun. 4937–4939 (2007).

  37. 37

    Walsh, P. J., Carney, M. J. & Bergman, R. G. Generation, dative ligand trapping, and nitrogen–nitrogen bond cleavage reactions of the first monomeric η1-hydrazido zirconocene complex, (Cp2Zr = NNPh2). A zirconium mediated synthesis of indoles. J. Am. Chem. Soc. 113, 6343–6345 (1991).

    CAS  Article  Google Scholar 

  38. 38

    Fagan, F. J. et al. Insertion of carbon monoxide into metal–nitrogen bonds. Synthesis, chemistry, structures, and structural dynamics of bis(pentamethylcyclopentadienyl) organoactinide dialkylamides and η2-carbamoyls. J. Am. Chem. Soc. 103, 2206–2220 (1981).

    CAS  Article  Google Scholar 

  39. 39

    Petz, W., Weller, F. & Avtomonov, E. V. Carbonyl insertion into zirconium–nitrogen bonds; synthesis and X-ray structure of a carbene complex composed of [Zr(NMe2)4]2 and three Fe(CO)5 units containing Fe → Zr donor–acceptor interactions. J. Organomet. Chem. 598, 403–408 (2000).

    CAS  Article  Google Scholar 

  40. 40

    Duncan, A. P. & Bergman, R. G. Selective transformations of organic compounds by imidozirconocene complexes. Chem. Rec. 2, 431–445 (2002).

    CAS  Article  PubMed  PubMed Central  Google Scholar 

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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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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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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)

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

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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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