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On-Surface Coupling Reactions with Extrinsic Catalysts

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On-Surface Synthesis II

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

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Abstract

On-surface coupling reactions have opened a novel route toward synthesizing various organic nanostructures on surfaces. In this chapter, we discuss the catalytic effects of Cu and Pd deposits in the on-surface Ullmann coupling and Sonogashira cross-coupling reactions. The stepwise reaction paths, intermediates, and activation energies are deliberated at a single molecular level using scanning tunneling microscopy (STM). Such studies offer mechanistic insights into the on-surface coupling reactions catalyzed by extrinsic metals.

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References

  1. Barth, J.V., Costantini, G., Kern, K.: Engineering atomic and molecular nanostructures at surfaces. Nature 437, 671–679 (2005). https://doi.org/10.1038/nature04166

    Article  CAS  Google Scholar 

  2. Slater, A.G., Perdigão, L.M.A., Beton, P.H., Champness, N.R.: Surface-based supramolecular chemistry using hydrogen bonds. Acc. Chem. Res. 47, 3417–3427 (2014). https://doi.org/10.1021/ar5001378

    Article  CAS  Google Scholar 

  3. Otero, R., Gallego, J.M., Vázquez de Parga, A.L., Martín, N., Miranda, R.: Molecular self-assembly at solid surfaces. Adv. Mater. 23, 5148–5176 (2011). https://doi.org/10.1002/adma.201102022

  4. Dong, L., Gao, Z., Lin, N.: Self-assembly of metal-organic coordination structures on surfaces. Prog. Surf. Sci. 91, 101–135 (2016). https://doi.org/10.1016/j.progsurf.2016.08.001

    Article  CAS  Google Scholar 

  5. Ullmann, F., Bielecki, J.: Synthesis in the biphenyl series. Ber. Dtsch. Chem. Ges. 34, 2174–2185 (1901)

    Article  CAS  Google Scholar 

  6. Dong, L., Liu, P.N., Lin, N.: Surface-activated coupling reactions confined on a surface. Acc. Chem. Res. 48, 2765–2774 (2015). https://doi.org/10.1021/acs.accounts.5b00160

    Article  CAS  Google Scholar 

  7. Fan, Q., Gottfried, J.M., Zhu, J.: Surface-catalyzed C-C covalent coupling strategies toward the synthesis of low-dimensional carbon-based nanostructures. Acc. Chem. Res. 48, 2484–2494 (2015). https://doi.org/10.1021/acs.accounts.5b00168

    Article  CAS  Google Scholar 

  8. Dil, H., Lobo-Checa, J., Laskowski, R., Blaha, P., Berner, S., Osterwalder, J., et al.: Surface trapping of atoms and molecules with dipole rings. Science 319, 1824–1826 (2008). https://doi.org/10.1126/science.1154179

  9. Schulz, F., Drost, R., Hämäläinen, S.K., Liljeroth, P.: Templated self-assembly and local doping of molecules on epitaxial hexagonal boron nitride. ACS Nano 7, 11121–11128 (2013). https://doi.org/10.1021/nn404840h

    Article  CAS  Google Scholar 

  10. Joshi, S., Bischoff, F., Koitz, R., Écija, D., Seufert, K., Seitsonen, A.P., et al.: Control of molecular organization and energy level alignment by an electronically nanopatterned boron nitride template. ACS Nano 8, 430–442 (2013). https://doi.org/10.1021/nn406024m

    Article  Google Scholar 

  11. Erler, P., Schmitt, P., Barth, N., Irmler, A., Bouvron, S., Huhn, T., et al.: Highly ordered surface self-assembly of Fe4 single molecule magnets. Nano Lett. 15, 4546–4552 (2015). https://doi.org/10.1021/acs.nanolett.5b01120

    Article  CAS  Google Scholar 

  12. Liu, L., Dienel, T., Widmer, R., Gröning, O.: Interplay between energy-level position and charging effect of manganese phthalocyanines on an atomically thin insulator. ACS Nano 9, 10125–10132 (2015). https://doi.org/10.1021/acsnano.5b03741

    Article  CAS  Google Scholar 

  13. Dienel, T., Gomez-Diaz, J., Seitsonen, A.P., Widmer, R., Iannuzzi, M., Radican, K., et al.: Dehalogenation and coupling of a polycyclic hydrocarbon on an atomically thin insulator. ACS Nano 8, 6571–6579 (2014). https://doi.org/10.1021/nn501906w

    Article  CAS  Google Scholar 

  14. Morchutt, C., Björk, J., Krotzky, S., Gutzler, R., Kern, K.: Covalent coupling via dehalogenation on Ni(111) supported boron nitride and graphene. Chem. Commun. 51, 2440–2443 (2015). https://doi.org/10.1039/c4cc07107g

  15. Zhao, W., Dong, L., Huang, C., Win, Z.M., Lin, N.: Cu- and Pd-catalyzed Ullmann reaction on a hexagonal boron nitride layer. Chem. Commun. 52, 13225–13228 (2016). https://doi.org/10.1039/C6CC05029H

    Article  CAS  Google Scholar 

  16. Sonogashira, K., Tohda, Y., Hagihara, N.: Convenient synthesis of acetylenes: catalytic substitutions of acetylenic hydrogen with bromoalkenes, iodoarenes and bromopyridines. Tetrahedron Lett. 16, 4467–4470 (1975). https://doi.org/10.1016/S0040-4039(00)91094-3

    Article  Google Scholar 

  17. Sonogashira, K.: Development of Pd–Cu catalyzed cross-coupling of terminal acetylenes with sp2-carbon halides. J. Organomet. Chem. 653, 46–49 (2002). https://doi.org/10.1016/S0022-328X(02)01158-0

    Article  CAS  Google Scholar 

  18. Kanuru, V.K., Kyriakou, G., Beaumont, S.K., Papageorgiou, A.C., Watson, D.J., Lambert, R.M.: Sonogashira coupling on an extended gold surface in vacuo: reaction of phenylacetylene with iodobenzene on Au(111). J. Am. Chem. Soc. 132, 8081–8086 (2010). https://doi.org/10.1021/ja1011542

    Article  CAS  Google Scholar 

  19. Sánchez-Sánchez, C., Yubero, F., González-Elipe, A.R., Feria, L., Sanz, J.F., Lambert, R.M.: The Flexible Surface Revisited: Adsorbate-Induced Reconstruction, Homocoupling, and Sonogashira Cross-Coupling on the Au(100) Surface. J. Phys. Chem. C 118, 11677–11684 (2014). https://doi.org/10.1021/jp501321u

    Article  Google Scholar 

  20. Sánchez-Sánchez, C., Orozco, N., Holgado, J.P., Beaumont, S.K., Kyriakou, G., Watson, D.J., et al.: Sonogashira cross-coupling and homocoupling on a silver surface: chlorobenzene and phenylacetylene on Ag(100). J. Am. Chem. Soc. 137, 940–947 (2015). https://doi.org/10.1021/ja5115584

    Article  Google Scholar 

  21. Zhang, R., Lyu, G., Li, D.Y., Liu, P.N., Lin, N.: Template-controlled sonogashira cross-coupling reactions on a Au(111) surface. Chem. Commun. 53, 1731–1734 (2017). https://doi.org/10.1039/c6cc10091k

  22. Adisoejoso, J., Lin, T., Shang, X.S., Shi, K.J., Gupta, A., Liu, P.N., et al.: 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, 4111–4116 (2014). https://doi.org/10.1002/chem.201304443

    Article  CAS  Google Scholar 

  23. 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, 13264–13267 (2011). https://doi.org/10.1021/ja204956b

    Article  CAS  Google Scholar 

  24. Yin, L., Liebscher, J.: carbon–carbon coupling reactions catalyzed by heterogeneous palladium catalysts. Chem. Rev. 107, 133–173 (2007). https://doi.org/10.1021/cr0505674

  25. Molnar, A.: Efficient, selective, and recyclable palladium catalysts in carbon-carbon coupling reactions. Chem. Rev. 111, 2251–2320 (2011). https://doi.org/10.1021/cr100355b

    Article  CAS  Google Scholar 

  26. Grill, L., Dyer, M., Lafferentz, L., Persson, M., Peters, M.V., Hecht, S.: Nano-architectures by covalent assembly of molecular building blocks. Nat. Nanotech. 2, 687–691 (2007). https://doi.org/10.1038/nnano.2007.346

    Article  CAS  Google Scholar 

  27. 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, 3576–3582 (2013). https://doi.org/10.1021/ja311890n

    Article  CAS  Google Scholar 

  28. Cai, J., Ruffieux, P., Jaafar, R., Bieri, M., Braun, T., Blankenburg, S., et al.: Atomically precise bottom-up fabrication of graphene nanoribbons. Nature 466, 470–473 (2010). https://doi.org/10.1038/nature09211

    Article  CAS  Google Scholar 

  29. Lafferentz, L., Eberhardt, V., Dri, C., Africh, C., Comelli, G., Esch, F., et al.: Controlling on-surface polymerization by hierarchical and substrate-directed growth. Nat. Chem. 4, 215–220 (2012). https://doi.org/10.1038/NCHEM.1242

    Article  CAS  Google Scholar 

  30. Meyers, J.M., Gellman, A.J.: Effect of substituents on the phenyl coupling reaction on Cu(111). Surf. Sci. 337, 40–50 (1995). https://doi.org/10.1016/0039-6028(95)00528-5

    Article  CAS  Google Scholar 

  31. 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). https://doi.org/10.1103/PhysRevB.84.125418

    Article  Google Scholar 

  32. Auwärter, W., Kreutz, T.J., Greber, T., Osterwalder, J.: XPD and STM investigation of hexagonal boron nitride on Ni(111). Surf. Sci. 429, 229–236 (1999). https://doi.org/10.1016/S0039-6028(99)00381-7

    Article  Google Scholar 

  33. 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, 12604–12609 (2010). https://doi.org/10.1021/jp102704q

    Article  CAS  Google Scholar 

  34. 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. 0, 4456–4458(2009). https://doi.org/10.1039/b906836h

  35. Hoffmann, M., Wilson, C.J., Odell, B., Anderson, H.L.: Template-directed synthesis of a π-conjugated porphyrin nanoring. Angew. Chem. Int. Ed. Engl. 46, 3122–3125 (2007). https://doi.org/10.1002/anie.200604601

    Article  CAS  Google Scholar 

  36. O’Sullivan, M.C., Sprafke, J.K., Kondratuk, D.V., Rinfray, C., Claridge, T.D.W., Saywell, A., et al.: Vernier templating and synthesis of a 12-porphyrin nano-ring. Nature 469, 72–75 (2011). https://doi.org/10.1038/nature09683

  37. Favereau, L., Cnossen, A., Kelber, J.B., Gong, J.Q., Oetterli, R.M., Cremers, J., et al.: Six-coordinate zinc porphyrins for template-directed synthesis of spiro-fused nanorings. J. Am. Chem. Soc. 137, 14256–14259 (2015). https://doi.org/10.1021/jacs.5b10126

    Article  CAS  Google Scholar 

  38. 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, 18526–18529 (2012). https://doi.org/10.1021/ja308480x

    Article  CAS  Google Scholar 

  39. Gao, H.-Y., Wagner, H., Zhong, D., Franke, J.-H., Studer, A., Fuchs, H.: Glaser coupling at metal surfaces. Angew. Chem. Int. Ed. 52, 4024–4028 (2013). https://doi.org/10.1002/anie.201208597

    Article  CAS  Google Scholar 

  40. Klappenberger, F., Zhang, Y.-Q., Björk, J., Klyatskay, S., Ruben, M., Barth, J.V.: On-surface synthesis of carbon-based scaffolds and nanomaterials using terminal alkynes. Acc. Chem. Res. 48, 2140–2150 (2015). https://doi.org/10.1021/acs.accounts.5b00174

    Article  CAS  Google Scholar 

  41. Zhou, H., Liu, J., Du, S., Zhang, L., Li, G., Zhang, Y., Tang, B.Z., Gao, H.-J.: Direct visualization of surface-assisted two-dimensional diyne polycyclotrimerization. J. Am. Chem. Soc. 136, 5567–5570 (2014). https://doi.org/10.1021/ja501308s

    Article  CAS  Google Scholar 

  42. Cirera, B., Zhang, Y.-Q., Björk, J., Klyatskaya, S., Chen, Z., Ruben, M., Barth, J.V., Klappenberger, F.: Synthesis of extended graphdiyne wires by vicinal surface templating. Nano Lett. 14, 1891–1897 (2014). https://doi.org/10.1021/nl4046747

    Article  CAS  Google Scholar 

  43. Cirera, B., Zhang, Y.-Q., Klyatskaya, S., Ruben, M., Klappenberger, F., Barth, J.V.: 2D self-assembly and catalytic homo-coupling of the terminal alkyne 1,4-Bis(3,5-diethynyl-phenyl)butadiyne-1,3 on Ag(111). ChemCatChem 5, 3281–3288 (2013). https://doi.org/10.1002/cctc.201300299

    Article  CAS  Google Scholar 

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Acknowledgements

This work was supported by Hong Kong RGC 16303514.

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Authors and Affiliations

  1. Department of Physics, The Hong Kong University of Science and Technology, Hong Kong, China

    Wei Zhao, Lei Dong, Ran Zhang & Nian Lin

  2. Department of Chemistry, University of Washington, Seattle, WA, 98195, USA

    Wei Zhao

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  1. Wei Zhao
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  2. Lei Dong
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  3. Ran Zhang
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  4. Nian Lin
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Correspondence to Nian Lin .

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Editors and Affiliations

  1. Donostia International Physics Center, San Sebastián, Spain

    Dimas G. de Oteyza

  2. Materials Physics Center, Centro de Física de Materiales CSIC-UPV/EHU, San Sebastián, Spain

    Celia Rogero

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Zhao, W., Dong, L., Zhang, R., Lin, N. (2018). On-Surface Coupling Reactions with Extrinsic Catalysts. In: de Oteyza, D., Rogero, C. (eds) On-Surface Synthesis II. Advances in Atom and Single Molecule Machines. Springer, Cham. https://doi.org/10.1007/978-3-319-75810-7_9

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