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.

  • Article
  • Published:

The role of bridging ligands in dinitrogen reduction and functionalization by uranium multimetallic complexes

Nature Chemistry volume 11, pages 154–160 (2019)Cite this article

Subjects

Abstract

Cooperativity between metal centres is identified as a crucial step in dinitrogen reduction both for the industrial Haber–Bosch process and for the natural fixation of nitrogen by nitrogenase enzymes, but the mechanism of N2 reduction remains poorly understood. This is in large part because multimetallic complexes that reduce and functionalize dinitrogen in the absence of strong alkali reducing agents are crucial to establish a structure–activity relationship, but remain extremely rare. Recently, we reported a multimetallic nitride-bridged diuranium(iii) complex capable of reducing and functionalizing dinitrogen. Here we show that an analogous complex assembled with an oxo instead of a nitride linker also effects the four-electron reduction of dinitrogen, but the reactivity of the resulting oxo–(N2) complex differs significantly from that of the nitride–(N2). Computational studies show a different bonding scheme for the dinitrogen where the bridging nitride does participate in the binding and consequent activation of N2, while the oxide does not.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Dinitrogen reduction and functionalization by a multimetallic uranium nitride.
Fig. 2: Synthesis and reactivity of oxo-bridged diuranium complexes.
Fig. 3: Molecular structure of 2, 3, 4 and 5.
Fig. 4: Magnetic susceptibility.
Fig. 5: Molecular orbitals of the different complexes.

Similar content being viewed by others

Data availability

All data generated and analysed during this study are included in this Article and its Supplementary Information or are available from the corresponding author upon reasonable request. Atomic coordinates and structure factors for the reported crystal structures have been deposited in the Cambridge Crystallographic Data Centre under accession codes CCDC 1821630 (2), 1821631 (3), 1821633 (4), 1821634 (5) and 1821632 (6).

References

  1. Burford, R. J. & Fryzuk, M. D. Examining the relationship between coordination mode and reactivity of dinitrogen. Nat. Rev. Chem. 1, 0026 (2017).

  2. Shaver, M. P. & Fryzuk, M. D. Activation of molecular nitrogen: coordination, cleavage and functionalization of N2 mediated by metal complexes. Adv. Synth. Catal. 345, 1061–1076 (2003).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  5. Wang, B. L. et al. Dinitrogen activation by dihydrogen and a PNP-ligated titanium complex. J. Am. Chem. Soc. 139, 1818–1821 (2017).

    Article  CAS  Google Scholar 

  6. Keane, A. J., Farrell, W. S., Yonke, B. L., Zavalij, P. Y. & Sita, L. R. Metal-mediated production of isocyanates, R3EN=C=O from dinitrogen, carbon dioxide, and R3ECl. Angew. Chem. Int. Ed. 54, 10220–10224 (2015).

    Article  CAS  Google Scholar 

  7. Knobloch, D. J., Lobkovsky, E. & Chirik, P. J. Dinitrogen cleavage and functionalization by carbon monoxide promoted by a hafnium complex. Nat. Chem. 2, 30–35 (2010).

    Article  CAS  Google Scholar 

  8. Falcone, M., Chatelain, L., Scopelliti, R., Zivkovic, I. & Mazzanti, M. Nitrogen reduction and functionalization by a multimetallic uranium nitride complex. Nature 547, 332–335 (2017).

    Article  CAS  Google Scholar 

  9. Anderson, J. S., Rittle, J. & Peters, J. C. Catalytic conversion of nitrogen to ammonia by an iron model complex. Nature 501, 84–87 (2013).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  11. MacLeod, K. C. & Holland, P. L. Recent developments in the homogeneous reduction of dinitrogen by molybdenum and iron. Nat. Chem. 5, 559–565 (2013).

    Article  CAS  Google Scholar 

  12. Haber, F. Verfahren zur Herstellung von Ammoniak durch katalytische Vereinigung von Stickstoff und Wasserstoff, zweckmäßig unter hohem Druch. German patent DE 229126 (1909).

  13. Cloke, G. F. N. & Hitchcock, P. B. Reversible binding and reduction of dinitrogen by a uranium (iii) pentalene complex. J. Am. Chem. Soc. 124, 9352–9353 (2002).

    Article  CAS  Google Scholar 

  14. Odom, A. L., Arnold, P. L. & Cummins, C. C. Heterodinuclear uranium/molybdenum dinitrogen complexes. J. Am. Chem. Soc. 120, 5836–5837 (1998).

    Article  CAS  Google Scholar 

  15. Mansell, S. M., Kaltsoyannis, N. & Arnold, P. L. Small molecule activation by uranium tris(aryloxides): experimental and computational studies of binding of N2, coupling of CO, and deoxygenation insertion of CO2 under ambient conditions. J. Am. Chem. Soc. 133, 9036–9051 (2011).

    Article  CAS  Google Scholar 

  16. Evans, W. J., Kozimor, S. A. & Ziller, J. W. A monometallic f element complex of dinitrogen: (C5Me5)3U(η1-N2). J. Am. Chem. Soc. 125, 14264–14265 (2003).

    Article  CAS  Google Scholar 

  17. Roussel, P. & Scott, P. Complex of dinitrogen with trivalent uranium. J. Am. Chem. Soc. 120, 1070–1071 (1998).

    Article  CAS  Google Scholar 

  18. Evans, W. J., Kozimor, S. A. & Ziller, J. W. Bis(pentamethylcyclopentadienyl) U(iii) oxide and U(iv) oxide carbene complexes. Polyhedron 23, 2689–2694 (2004).

    Article  CAS  Google Scholar 

  19. Larch, C. P., Cloke, F. G. N. & Hitchcock, P. B. Activation and reduction of diethyl ether by low valent uranium: formation of the trimetallic, mixed valence uranium oxo species [U(CpRR’)(µ-I)2]3(µ3-O) (CpRR’ = C5Me5, C5Me4H, C5H4SiMe3). Chem. Commun. 82–84 (2008).

  20. Castro-Rodriguez, I., Olsen, K., Gantzel, P. & Meyer, K. Uranium complexes supported by an aryloxide functionalised triazacyclononane macrocycle: synthesis and characterisation of a six-coordinate U(iii) species and insights into its reactivity. Chem. Commun. 2764–2765 (2002).

  21. Wang, J. X., Gurevich, Y., Botoshansky, M. & Eisen, M. S. Unique σ-bond metathesis of silylalkynes promoted by an ansa-dimethylsilyl and oxo-bridged uranium metallocene. J. Am. Chem. Soc. 128, 9350–9351 (2006).

    Article  CAS  Google Scholar 

  22. Lam, O. P., Bart, S. C., Kameo, H., Heinemann, F. W. & Meyer, K. Insights into the mechanism of carbonate formation through reductive cleavage of carbon dioxide with low-valent uranium centers. Chem. Commun. 46, 3137–3139 (2010).

    Article  CAS  Google Scholar 

  23. Castro, L., Lam, O. P., Bart, S. C., Meyer, K. & Maron, L. Carbonate formation from CO2 via oxo versus oxalate pathway: theoretical investigations into the mechanism of uranium-mediated carbonate formation. Organometallics 29, 5504–5510 (2010).

    Article  CAS  Google Scholar 

  24. Fortier, S., Brown, J. L., Kaltsoyannis, N., Wu, G. & Hayton, T. W. Synthesis, molecular and electronic structure of UV(O)[N(SiMe3)2]3. Inorg. Chem. 51, 1625–1633 (2012).

    Article  CAS  Google Scholar 

  25. Berthet, J. C. et al. Synthesis and crystal structure of the oxo-bridged bimetallic organouranium complex [{(Me3SiC5H4)3U2}µ-O]. J. Organomet. Chem. 408, 335–341 (1991).

    Article  CAS  Google Scholar 

  26. Schmidt, A. C., Nizovtsev, A. V., Scheurer, A., Heinemann, F. W. & Meyer, K. Uranium-mediated reductive conversion of CO2 to CO and carbonate in a single-vessel, closed synthetic cycle. Chem. Commun. 48, 8634–8636 (2012).

    Article  CAS  Google Scholar 

  27. Frey, A. S. P., Cloke, F. G. N., Coles, M. P. & Hitchcock, P. B. UIII-induced reductive co-coupling of NO and CO to form U(iv) cyanate and oxo derivates. Chem. Eur. J. 16, 9446–9448 (2010).

    Article  CAS  Google Scholar 

  28. Avens, L. R., Barnhart, D. M., Burns, C. J., McKee, S. D. & Smith, W. H. Oxidation chemistry of a U(iii) aryloxide. Inorg. Chem. 33, 4245–4254 (1994).

    Article  CAS  Google Scholar 

  29. Falcone, M., Kefalidis, C. E., Scopelliti, R., Maron, L. & Mazzanti, M. Facile CO cleavage by a multimetallic CsU2 nitride complex. Angew. Chem. Int. Ed. 55, 12290–12294 (2016).

    Article  CAS  Google Scholar 

  30. Falcone, M., Chatelain, L. & Mazzanti, M. Nucleophilic reactivity of a nitride-bridged diuranium(iv) complex: CO2 and CS2 functionalization. Angew. Chem. Int. Ed. 55, 4074–4078 (2016).

    Article  CAS  Google Scholar 

  31. Mougel, V. et al. Siloxides as supporting ligands in uranium(iii)-mediated small-molecule activation. Angew. Chem. Int. Ed. 51, 12280–12284 (2012).

    Article  CAS  Google Scholar 

  32. Tskhovrebov, A. G., Vuichoud, B., Solari, E., Scopelliti, R. & Severin, K. Adducts of nitrous oxide and N-heterocyclic carbenes: syntheses, structures, and reactivity. J. Am. Chem. Soc. 135, 9486–9492 (2013).

    Article  CAS  Google Scholar 

  33. Tskhovrebov, A. G., Solari, E., Wodrich, M. D., Scopelliti, R. & Severin, K. Covalent capture of nitrous oxide by N-heterocyclic carbenes. Angew. Chem. Int. Ed. 51, 232–234 (2012).

    Article  CAS  Google Scholar 

  34. Palluccio, T. D. et al. Thermodynamic and kinetic study of cleavage of the N–O bond of N-oxides by a vanadium(iii) complex: enhanced oxygen atom transfer reaction rates for adducts of nitrous oxide and mesityl nitrile oxide. J. Am. Chem. Soc. 135, 11357–11372 (2013).

    Article  CAS  Google Scholar 

  35. Huynh, M. H. V., White, P. S., Carter, C. A. & Meyer, T. J. Formation and reactivity of the osmium(iv)–cyanoimido complex OsIV(bpy)(Cl)3(NCN)−. Angew. Chem. Int. Ed. 40, 3037–3039 (2001).

    Article  CAS  Google Scholar 

  36. Kajitani, H., Tanabe, Y., Kuwata, S., Iwasaki, M. & Ishii, Y. A cyanamido-bridged diiridium complex: a reactive building block for polynuclear cyanamido complexes. Organometallics 24, 2251–2254 (2005).

    Article  CAS  Google Scholar 

  37. Mindiola, D. J. et al. Bimetallic µ-cyanoimide complexes prepared by NCN group transfer. Chem. Commun. 125–126 (2001).

  38. Kindra, D. R. & Evans, W. J. Magnetic susceptibility of uranium complexes. Chem. Rev. 114, 8865–8882 (2014).

    Article  CAS  Google Scholar 

  39. Pool, J. A., Bernskoetter, W. H. & Chirik, P. J. On the origin of dinitrogen hydrogenation promoted by [(η5-C5Me4H)2Zr]2(µ2,η2,η2-N2). J. Am. Chem. Soc. 126, 14326–14327 (2004).

    Article  CAS  Google Scholar 

  40. La Pierre, H. S. & Meyer, K. in Progress in Inorganic Chemistry Vol. 58 (ed. Karlin, K. D.) 303–415 (Wiley, Hoboken, 2014).

  41. Fryzuk, M. D., Haddad, T. S. & Rettig, S. J. Reduction of dinitrogen by a zirconium phosphine complex to form a side-on-bridging N2 ligand. Crystal structure of {[(Pri 2PCH2SiMe2)2N]ZrCl}2(µ-η2:η2-N2). J. Am. Chem. Soc. 112, 8185–8186 (1990).

    Article  CAS  Google Scholar 

  42. Ohki, Y. & Fryzuk, M. D. Dinitrogen activation by group 4 metal complexes. Angew. Chem. Int. Ed. 46, 3180–3183 (2007).

    Article  CAS  Google Scholar 

  43. Tanabe, Y., Kuwata, S. & Ishii, Y. Syntheses and skeletal transformations of NCNH- and NCN-bridged tetrairidium(iii) cages. J. Am. Chem. Soc. 124, 6528–6529 (2002).

    Article  CAS  Google Scholar 

  44. Schmidt, A.-C., Heinemann, F. W., Lukens, W. W. Jr & Meyer, K. Molecular and electronic structure of dinuclear uranium bis-μ-oxo complexes with diamond core structural motifs. J. Am. Chem. Soc. 136, 11980–11993 (2014).

    Article  CAS  Google Scholar 

  45. Reynolds, J. G., Zalkin, A., Templeton, D. H. & Edelstein, N. M. Syntheses and crystal structures of tetrakis(diphenylamido)uranium(iv) and bis(µ-oxo-tris(diphenylamido)uranium(iv)lithium diethyl etherate. Inorg. Chem. 16, 1090–1096 (1977).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors acknowledge support from the Swiss National Science Foundation (grant nos. 200021_162430 and 200021_178793) and from the Ecole Polytechnique Fédérale de Lausanne (EPFL). The authors thank E. Solari for carrying out the elemental analyses, L. Y. M. Eymann for synthesis of the IMesN2O adduct and R. Scopelliti for important contributions to the X-ray single-crystal structure analyses.

Author information

Authors and Affiliations

  1. Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), Lausanne, Switzerland

    Marta Falcone, Luciano Barluzzi, Julie Andrez, Farzaneh Fadaei Tirani, Alberto Fabrizio, Clemence Corminboeuf, Kay Severin & Marinella Mazzanti

  2. Laboratory for Quantum Magnetism, Institute of Physics, Ecole Polytechnique Fédérale de Lausanne (EPFL), Lausanne, Switzerland

    Ivica Zivkovic

Authors
  1. Marta Falcone
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Luciano Barluzzi
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Julie Andrez
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Farzaneh Fadaei Tirani
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Ivica Zivkovic
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Alberto Fabrizio
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Clemence Corminboeuf
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Kay Severin
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Marinella Mazzanti
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

M.F. and L.B. carried out the synthetic experiments and analysed the experimental data. J.A. performed preliminary experiments and characterized the U–O–U complexes. F.F.T. carried out the X-ray single-crystal structure analyses. I.Z. measured and analysed the magnetic data. A.F. and C.C. performed the theoretical computations. K.S. contributed to the identification of a new route to oxo complexes. M.M. originated the central idea, coordinated the work and analysed the experimental data. M.M., M.F. and L.B. wrote the manuscript.

Corresponding author

Correspondence to Marinella Mazzanti.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary Methods, Supplementary Characterization, Supplementary Computational analysis

Crystallographic data

CIF for compound 2; CCDC reference: 1821630.

Crystallographic data

CIF for compound 3; CCDC reference: 1821631.

Crystallographic data

CIF for compound 4; CCDC reference: 1821633.

Crystallographic data

CIF for compound 5; CCDC reference: 1821634.

Crystallographic data

CIF for compound 6; CCDC reference: 1821632.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Falcone, M., Barluzzi, L., Andrez, J. et al. The role of bridging ligands in dinitrogen reduction and functionalization by uranium multimetallic complexes. Nature Chem 11, 154–160 (2019). https://doi.org/10.1038/s41557-018-0167-8

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41557-018-0167-8

This article is cited by

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