Skip to main content
SpringerLink
Log in

Transition Metals Trigger On-Surface Ullmann Coupling Reaction: Intermediate, Catalyst and Template

  • Conference paper
  • First Online:
On-Surface Synthesis

Part of the book series: Advances in Atom and Single Molecule Machines ((AASMM))

Abstract

In this chapter, we report on our recent studies of on-surface Ullmann coupling reaction and focus on the roles of the transition metals in the reaction. First, we discuss an organometallic intermediate state, which separates the reaction into two steps. Next, we examine the catalytic efficiency of Cu, Au, Ag, Pt, and Pd in the reaction. We analyze the bond formation yields when the reaction takes place in the presence of these metals. In particular, we determine the rate constants and activation energy of Cu- and Pd-catalyzed reaction. In the last part, we demonstrate a strategy of using metal coordination template to steer the reaction toward specific products.

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Log in via an institution
Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 169.00
Price excludes VAT (USA)
  • Available as EPUB and PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 219.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info
Hardcover Book
USD 219.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

References

  1. Barth, J.V.: Molecular architectonic on metal surfaces. Annu. Rev. Phys. Chem. 58, 375 (2007)

    Article  CAS  Google Scholar 

  2. De Feyter, S., Miura, A., Yao, S., Chen, Z., Würthner, F., Jonkheijm, P., Schenning, A.P.H.J., Meijer, E.W., De Schryver, F.C.: Two-dimensional self-assembly into multicomponent hydrogen-bonded nanostructures. Nano Lett. 5, 77 (2005)

    Article  Google Scholar 

  3. Barth, J.V., Weckesser, J., Trimarchi, G., Vladimirova, M., De Vita, A., Cai, C., Brune, H., Günter, P., Kern, K.: Stereochemical effects in supramolecular self-assembly at surfaces: 1-D versus 2-D enantiomorphic ordering for PVBA and PEBA. J. Am. Chem. Soc. 124, 7991 (2002)

    Article  CAS  Google Scholar 

  4. Cañas Ventura, M.E., Xiao, W., Wasserfallen, D., Müllen, K., Brune, H., Barth, J.V., Fasel, R.: Self-assembly of periodic bicomponent wires and ribbons. Angew. Chem. Int. Ed. 46, 1814 (2007)

    Google Scholar 

  5. Berger, G., Soubhye, J., Meyer, F.: Halogen bonding in polymer science: from crystal engineering to functional supramolecular polymers and materials. Polym. Chem. 6, 3559 (2015)

    Article  CAS  Google Scholar 

  6. Stepanow, S., Lin, N., Barth, J.V.: Modular assembly of low-dimensional coordination architectures on metal surfaces. J. Phys. Cond. Mat. 20, 184002 (2008)

    Article  Google Scholar 

  7. Ullmann, F., Bielecki, J.: Ueber Synthesen in der Biphenylreihe. Ber. Dtsch. Chem. Ges. 34, 2174 (1901)

    Article  CAS  Google Scholar 

  8. Grill, L., Dyer, M., Lafferentz, L., Persson, M., Peters, M.V., Hecht, S.: Nano-architectures by covalent assembly of molecular building blocks. Nature Nanotech. 2, 687 (2007)

    Article  CAS  Google Scholar 

  9. Lipton Duffin, J.A., Miwa, J.A., Kondratenko, M., Cicoira, F., Sumpter, B.G., Meunier, V., Perepichka, D.F., Rosei, F.: Step-by-step growth of epitaxially aligned polythiophene by surface-confined reaction. PNAS 107, 11200 (2010)

    Google Scholar 

  10. Cai, J., Ruffieux, P., Jaafar, R., Bieri, M., Braun, T., Blankenburg, S., Muoth, M., Seitsonen, A.P., Saleh, M., Feng, X., Müllen, K., Fasel, R.: Atomically precise bottom-up fabrication of graphene nanoribbons. Nature 466, 470 (2010)

    Article  CAS  Google Scholar 

  11. Gutzler, R., Walch, H., Eder, G., Kloft, S., Heckl, W.M., Lackinger, M.: Surface mediated synthesis of 2D covalent organic frameworks: 1,3,5-tris(4-bromophenyl)benzene on graphite (001), Cu (111), and Ag (110). Chem. Commun. 4456 (2009)

    Google Scholar 

  12. Lafferentz, L., Eberhardt, V., Dri, C., Africh, C., Comelli, G., Esch, F., Hecht, S., Grill, L.: Controlling on-surface polymerization by hierarchical and substrate-directed growth. Nature Chem. 4, 215 (2012)

    Article  CAS  Google Scholar 

  13. Bieri, M., Nguyen, M.-T., Gröning, O., Cai, J., Treier, M., Aït-Mansour, K., Ruffieux, P., Pignedoli, C.A., Passerone, D., Kastler, M., Müllen, K., Fasel, R.: Two-dimensional polymer formation on surfaces: insight into the roles of precursor mobility and reactivity. J. Am. Chem. Soc. 132, 16669 (2010)

    Article  CAS  Google Scholar 

  14. El Garah, M., MacLeod, J.M., Rosei, F.: Covalently bonded networks through surface-confined polymerization. Surf. Sci. 613, 6 (2013)

    Article  Google Scholar 

  15. Lipton Duffin, J.A., Ivasenko, O., Perepichka, D.F., Rosei, F.: Synthesis of polyphenylene molecular wires by surface‐confined polymerization. Small 5, 592 (2009)

    Google Scholar 

  16. McCarty, G.S., Weiss, P.S.: Formation and manipulation of protopolymer chains. J. Am. Chem. Soc. 126, 16772 (2004)

    Article  CAS  Google Scholar 

  17. Walch, H., Gutzler, R., Sirtl, T., Eder, G., Lackinger, M.: Material-and orientation-dependent reactivity for heterogeneously catalyzed carbon-bromine bond homolysis. J. Phys. Chem. C 114, 12604 (2010)

    Article  CAS  Google Scholar 

  18. Blake, M.M., Nanayakkara, S.U., Claridge, S.A., Fernandez-Torres, L.C., Sykes, E.C.H., Weiss, P.S.: Identifying reactive intermediates in the Ullmann coupling reaction by scanning tunneling microscopy and spectroscopy. J. Phys. Chem. A 113, 13167 (2009)

    Google Scholar 

  19. Sykes, E.C.H., Han, P., Kandel, S.A., Kelly, K.F., McCarty, G.S., Weiss, P.S.: Substrate-mediated interactions and intermolecular forces between molecules adsorbed on surfaces. Acc. Chem. Res. 36, 945 (2003)

    Article  CAS  Google Scholar 

  20. Wang, W., Shi, X., Wang, S., Van Hove, M.A., Lin, N.: Single-molecule resolution of an organometallic intermediate in a surface-supported ullmann coupling reaction. J. Am. Chem. Soc. 133, 13264 (2011)

    Article  CAS  Google Scholar 

  21. Wang, S., Wang, W., Lin, N.: Resolving band-structure evolution and defect-induced states of single conjugated oligomers by scanning tunneling microscopy and tight-binding calculations. Phys. Rev. Lett. 106, 206803 (2011)

    Article  Google Scholar 

  22. Chung, K.-H., Koo, B.-G., Kim, H., Yoon, J.K., Kim, J.-H., Kwon, Y.-K., Kahng, S.-J.: Electronic structures of one-dimensional metal-molecule hybrid chains studied using scanning tunneling microscopy and density functional theory. Phys. Chem. Chem. Phys. 14, 7304 (2012)

    Article  CAS  Google Scholar 

  23. Blunt, M.O., Russell, J.C., Champness, N.R., Beton, P.H.: Templating molecular adsorption using a covalent organic framework. Chem. Comm. 46, 7157 (2010)

    Article  CAS  Google Scholar 

  24. Russell, J.C., Blunt, M.O., Garfitt, J.M., Scurr, D.J., Alexander, M., Champness, N.R., Beton, P.H.: Dimerization of tri(4-bromophenyl)benzene by aryl-aryl coupling from solution on a gold surface. J. Am. Chem. Soc. 133, 4220 (2011)

    Article  CAS  Google Scholar 

  25. Park, J., Kim, K.Y., Chung, K.-H., Yoon, J.K., Kim, H., Han, S., Kahng, S.-J.: Interchain interactions mediated by Br adsorbates in arrays of metal-organic hybrid chains on Ag(111). J. Phys. Chem. C 115, 14834 (2011)

    Article  CAS  Google Scholar 

  26. Wintterlin, J., Volkening, S., Janssens, T., Zambelli, T., Ertl, G.: Atomic and macroscopic reaction rates of a surface-catalyzed reaction. Science 278, 1931 (1997)

    Article  CAS  Google Scholar 

  27. Adisoejoso, J., Lin, T., Shang, X.S., Shi, K.J., Gupta, A., Liu, P.N., Lin, N.: A single-molecule-level mechanistic study of Pd-catalyzed and Cu-catalyzed homocoupling of aryl bromide on an Au(111) surface. Chem. Eur. J. 20, 4111 (2014)

    Article  CAS  Google Scholar 

  28. Molnar, A.: Efficient, selective, and recyclable palladium catalysts in carbon-carbon coupling reactions. Chem. Rev. 111, 2251 (2011)

    Article  CAS  Google Scholar 

  29. Yin, L., Liebscher, J.: Carbon-carbon coupling reactions catalyzed by heterogeneous palladium catalysts. Chem. Rev. 107, 133 (2007)

    Article  CAS  Google Scholar 

  30. Nguyen, M.-T., Pignedoli, C.A., Passerone, D.: An ab initio insight into the Cu(111)-mediated Ullmann reaction. Phys. Chem. Chem. Phys. 13, 154 (2011)

    Article  CAS  Google Scholar 

  31. Meyers, J.M., Gellman, A.J.: Effect of substituents on the phenyl coupling reaction on Cu(111). Surf. Sci. 337, 40 (1995)

    Article  CAS  Google Scholar 

  32. Li, Y., Lin, N.: Combined scanning tunneling microscopy and kinetic Monte Carlo study on kinetics of Cu-coordinated pyridyl-porphyrin supramolecular self-assembly on a Au(111) surface. Phys. Rev. B 84, 125418 (2011)

    Article  Google Scholar 

  33. Zhong, D., Franke, J.-H., Podiyanachari, S.K., Blömker, T., Zhang, H., Kehr, G., Erker, G., Fuchs, H., Chi, L.: Linear alkane polymerization on a gold surface. Science 334, 213 (2011)

    Article  CAS  Google Scholar 

  34. Dienstmaier, J.F., Medina, D.D., Dogru, M., Knochel, P., Bein, T., Heckl, W.M., Lackinger, M.: Isoreticular two-dimensional covalent organic frameworks synthesized by on-surface condensation of diboronic acids. ACS Nano 6, 7234 (2012)

    Article  CAS  Google Scholar 

  35. Dienstmaier, J.F., Gigler, A.M., Goetz, A.J., Knochel, P., Bein, T., Lyapin, A., Reichlmaier, S., Heckl, W.M., Lackinger, M.: Synthesis of well-ordered COF monolayers: surface growth of nanocrystalline precursors versus direct on-surface polycondensation. ACS Nano 5, 9737 (2011)

    Article  CAS  Google Scholar 

  36. Guan, C.-Z., Wang, D., Wan, L.-J.: Construction and repair of highly ordered 2D covalent networks by chemical equilibrium regulation. Chem. Comm. 48, 2943 (2012)

    Article  CAS  Google Scholar 

  37. Weigelt, S., Bombis, C., Busse, C., Knudsen, M.M., Gothelf, K.V., Lægsgaard, E., Besenbacher, F., Linderoth, T.R.: Molecular self-assembly from building blocks synthesized on a surface in ultrahigh vacuum: kinetic control and topo-chemical reactions. ACS Nano 2, 651 (2008)

    Article  CAS  Google Scholar 

  38. Lafferentz, L., Eberhardt, V., Dri, C., Africh, C., Comelli, G., Esch, F., Hecht, S., Grill, L.: Controlling on-surface polymerization by hierarchical and substrate-directed growth. Nature Chem. 4, 215 (2012)

    Article  CAS  Google Scholar 

  39. Anderson, S., Anderson, H.L., Sanders, J.K.M.: Expanding roles for templates in synthesis. Acc. Chem. Res. 26, 469 (1993)

    Article  CAS  Google Scholar 

  40. Thompson, M.C., Busch, D.H.: Reactions of coordinated ligands. IX. Utilization of the template hypothesis to synthesize macrocyclic ligands in situ. J. Am. Chem. Soc. 86, 3651 (1964)

    Article  CAS  Google Scholar 

  41. Sprafke, J.K., Kondratuk, D.V., Wykes, M., Thompson, A.L., Hoffmann, M., Drevinskas, R., Chen, W.-H., Yong, C.K., Kärnbratt, J., Bullock, J.E., Malfois, M., Wasielewski, M.R., Albinsson, B., Herz, L.M., Zigmantas, D., Beljonne, D., Anderson, H.L.: Belt-shaped π-systems: relating geometry to electronic structure in a six-porphyrin nanoring. J. Am. Chem. Soc. 133, 17262 (2011)

    Article  CAS  Google Scholar 

  42. Lin, T., Shang, X.S., Adisoejoso, J., Liu, P.N., Lin, N.: Steering on-surface polymerization with metal-directed template. J. Am. Chem. Soc. 135, 3576 (2013)

    Article  CAS  Google Scholar 

  43. Adisoejoso, J., Li, Y., Liu, J., Liu, P.N., Lin, N.: Two-dimensional metallo-supramolecular polymerization: toward size-controlled multi-strand polymers. J. Am. Chem. Soc. 134, 18526 (2012)

    Article  CAS  Google Scholar 

  44. Nagahama, S., Matsumoto, A.: Two-dimensional polymer synthesis through the topochemical polymerization of alkylenediammonium muconate as a multifunctional monomer. J. Polym. Sci. Part A: Polym. Chem. 42, 3922 (2004)

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Physics, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China

    L. Dong, S. Wang, W. Wang, C. Chen, T. Lin, J. Adisoejoso & N. Lin

Authors
  1. L. Dong
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. S. Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. W. Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. C. Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. T. Lin
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. J. Adisoejoso
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. N. Lin
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to N. Lin .

Editor information

Editors and Affiliations

  1. CEMES-CNRS, Toulouse, France

    André Gourdon

Rights and permissions

Reprints and permissions

Copyright information

© 2016 Springer International Publishing Switzerland

About this paper

Cite this paper

Dong, L. et al. (2016). Transition Metals Trigger On-Surface Ullmann Coupling Reaction: Intermediate, Catalyst and Template. In: Gourdon, A. (eds) On-Surface Synthesis. Advances in Atom and Single Molecule Machines. Springer, Cham. https://doi.org/10.1007/978-3-319-26600-8_2

Download citation

Publish with us

Policies and ethics

Search

Navigation