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Olefin Metathesis With Ruthenium-Arene Catalysts Bearing N-Heterocyclic Carbene Ligands

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Metathesis Chemistry

Part of the book series: NATO Science Series ((NAII,volume 243))

In this chapter, we summarize the main results of our investigations on the ring-opening metathesis polymerization (ROMP) of cyclooctene catalyzed by various ruthenium (Ru)–arene complexes bearing imidazolin-2-ylidene, imidazolidin- 2-ylidene, or triazolin-5-ylidene ligands. Three major findings emerged from this study. First, we underscored the intervention of a photochemical activation step due to visible light illumination. Second, we established that the presence of an endocyclic double bond in the carbene ligand central heterocycle was not crucial to achieve high catalytic efficiencies. Third, we demonstrated that ortho-metallation of the N-heterocyclic carbene (NHC) ligand by the Ru center led to inactive catalysts.

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References

  1. Le Bozec, H., Touchard, D., Dixneuf, P.H., Organometallic chemistry of arene ruthenium and osmium complexes, Adv. Organomet. Chem. 1989, 29:163-247.

    Article  CAS  Google Scholar 

  2. Bennett, M.A., Recent advances in the chemistry of arene complexes of ruthenium(0) and ruthenium(II), Coord. Chem. Rev. 1997, 166:225-254.

    Article  CAS  Google Scholar 

  3. Pigge, F.C., Coniglio, J.J., Stoichiometric applications of η6-arene ruthenium(II) complexes in organic chemistry, Curr. Org. Chem. 2001, 5:757-784.

    Article  CAS  Google Scholar 

  4. Rigby, J.H., Kondratenko, M.A., Arene complexes as catalysts, Top. Organonomet. Chem. 2004, 7:181-204.

    CAS  Google Scholar 

  5. Küçükbay, H., Çetinkaya, B., Guesmi, S., Dixneuf, P.H., New (carbene)ruthenium-arene complexes: preparation and uses in catalytic synthesis of furans, Organometallics 1996, 15:2434-2439.

    Article  Google Scholar 

  6. Çetinkaya, B., Özdemir, I., Dixneuf, P.H., Synthesis and catalytic properties of N-functionalized carbene complexes of rhodium(I) and ruthenium(II), J. Organomet. Chem. 1997, 534:153-158.

    Article  Google Scholar 

  7. Fürstner, A., Müller, T., Efficient total synthesis of resin glycosides and analogues by ring-closing olefin metathesis, J. Am. Chem. Soc.1999, 121:7814-7821.

    Article  Google Scholar 

  8. Castarlenas, R., Dixneuf, P.H., Highly active catalysts in alkene metathesis: first observed transformation of allenylidene into indenylidene via alkenyl-carbyne-ruthenium species, Angew. Chem. Int. Edit. 2003, 42:4524-4527.

    Article  CAS  Google Scholar 

  9. Castarlenas, R., Eckert, M., Dixneuf, P.H., Alkenylcarbene ruthenium arene complexes as initiators of alkene metathesis: an enyne creates a catalyst that promotes its selective transformation, Angew. Chem. Int. Edit. 2005, 44: 2576-2579.

    Article  CAS  Google Scholar 

  10. Yiğit, M., Yiğit, B., Özdemir, I., Çetinkaya, E., Çetinkaya, B., Active ruthenium-(N-heterocyclic carbene) complexes for hydrogenation of ketones, Appl. Organomet. Chem. 2006, 20:322-327.

    Article  Google Scholar 

  11. Quebatte, L., Haas, M., Solari, E., Scopelliti, R., Nguyen, Q.T., Severin, K., Atom-transfer radical reactions under mild conditions with [{RuCl2(1,3,5-C6H3iPr3)}2] and PCy3 as the catalyst precursors, Angew. Chem. Int. Edit. 2005, 44:1084-1088.

    Article  CAS  Google Scholar 

  12. Hafner, A., Mühlebach, A., van der Schaaf, P.A., One-component catalysts for thermal and photoinduced ring opening metathesis polymerization, Angew. Chem. Int. Edit. 1997, 36:2121-2124.

    Article  CAS  Google Scholar 

  13. Fürstner, A., Ackermann, L., A most user-friendly protocol for ring closing metathesis reactions, Chem. Commun. 1999, 95-96.

    Google Scholar 

  14. Fürstner, A., Liebl, M., Lehmann, C.W., Picquet, M., Kunz, R., Bruneau, C., Touchard, D., Dixneuf, P.H., Cationic ruthenium allenylidene complexes as catalysts for ring closing olefin metathesis, Chem. Eur. J. 2000, 6:1847-1857.

    Article  Google Scholar 

  15. Stumpf, A.W., Saive, E., Demonceau, A., Noels, A.F., Ruthenium-based catalysts for the ring-opening metathesis polymerization of low-strain cyclic olefins and of functionalised derivatives of norbornene and cyclooctene, Chem. Commun. 1995, 1127-1128.

    Google Scholar 

  16. Demonceau, A., Stumpf, A.W., Saive, E., Noels, A.F., Novel ruthenium-based catalyst systems for the ring-opening metathesis polymerization of low-strain cyclic olefins, Macromolecules 1997, 30:3127-3136.

    Article  CAS  Google Scholar 

  17. Arduengo, A.J. III, Harlow, R.L., Kline, M., A stable crystalline carbene, J. Am. Chem. Soc. 1991, 113:361-363.

    Article  CAS  Google Scholar 

  18. Arduengo, A.J. III, Rasika Dias, H.V., Harlow, R.L., Kline, M., Electronic stabilization of nucleophilic carbenes, J. Am. Chem. Soc. 1992, 114:5530-5534.

    Article  CAS  Google Scholar 

  19. Arduengo, A.J. III, Krafczyk, R., Schmutzler, R., Craig, H.A., Goerlich, J.R., Marshall, W.J., Unverzagt, M., Imidazolylidenes, imidazolinylidenes and imidazolidines, Tetrahedron 1999, 55:14523-14534.

    Article  CAS  Google Scholar 

  20. Arduengo, A.J. III, Looking for stable carbenes: the difficulty in starting anew, Acc. Chem. Res. 1999, 32:913-921.

    Article  CAS  Google Scholar 

  21. Bourrisou, D., Guerret, O., Gabbaï, F.P., Bertrand, G., Stable carbenes, Chem. Rev. 2000, 100:39-91.

    Google Scholar 

  22. Jafarpour, L., Nolan, S.P., Transition-metal systems bearing a nucleophilic carbene ancillary ligand: from thermochemistry to catalysis, Adv. Organomet. Chem. 2001, 46:181-222.

    Article  Google Scholar 

  23. Herrmann, W.A., Weskamp, T., Böhm, V.P.W., Metal complexes of stable carbenes, Adv. Organomet. Chem. 2002, 48:1-69.

    Article  Google Scholar 

  24. Herrmann, W.A., N-heterocyclic carbenes: a new concept in organometallic catalysis, Angew. Chem. Int. Edit. 2002, 41:1290-1309.

    Article  CAS  Google Scholar 

  25. Dragutan, I., Dragutan, V., Delaude, L., Demonceau, A., N-Heterocyclic carbenes as highly efficient ancillary ligands in homogeneous and immobi-lized metathesis ruthenium catalytic systems, Arkivoc (x) 2005, 206-253.

    Google Scholar 

  26. Nair, V., Bindu, S., Sreekumar, V., N-heterocyclic carbenes: reagents, not just ligands!, Angew. Chem. Int. Edit. 2004, 43:5130-5135.

    Article  CAS  Google Scholar 

  27. Enders, D., Balensiefer, T., Nucleophilic carbenes in asymmetric organocatalysis, Acc. Chem. Res. 2004, 37:534-541.

    Article  CAS  Google Scholar 

  28. César, V., Bellemin-Laponnaz, S., Gade, L.H., Chiral N-heterocyclic carbenes as stereodirecting ligands in asymmetric catalysis, Chem. Soc. Rev. 2004, 33:619-636.

    Article  Google Scholar 

  29. Herrmann, W.A., Köcher, C., N-heterocyclic carbenes, Angew. Chem. Int. Edit. 1997, 36:2162-2187.

    Article  CAS  Google Scholar 

  30. Enders, D., Breuer, K., Raabe, G., Runsink, J., Teles, J.H., Melder, J.-P., Ebel, K., Brode, S., Preparation, structure, and reactivity of 1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene, a new stable carbene, Angew. Chem. Int. Edit. 1995, 34:1021-1023.

    Article  CAS  Google Scholar 

  31. Enders, D., Breuer, K., Kallfass, U., Balensiefer, T., Preparation and application of 1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene, a stable carbene, Synthesis 2003, 1292-1295.

    Google Scholar 

  32. Enders, D., Gielen, H., Synthesis of chiral triazolinylidene and imidazo-linylidene transition metal complexes and first application in asymmetric catalysis, J. Organomet. Chem. 2001, 617-618:70-80.

    Article  CAS  Google Scholar 

  33. Delaude, L., Demonceau, A., Noels, A.F., Synthesis and application of new N-heterocyclic carbene ruthenium complexes in catalysis: a case study, Curr. Org. Chem. 2006, 10:203-215.

    Article  CAS  Google Scholar 

  34. Herrmann, W.A., Köcher, C., Goossen, L.J., Artus, G.R.J., Heterocyclic carbenes: a high-yielding synthesis of novel, functionalized N-heterocyclic carbenes in liquid ammonia, Chem. Eur. J. 1996, 2:1627-1636.

    Article  CAS  Google Scholar 

  35. Jafarpour, L., Huang, J., Stevens, E.D., Nolan, S.P.,(p-cymene)RuLCl2 (L=1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene and1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) and related complexes as ring closing metathesis catalysts, Organometallics 1999, 18:3760-3763.

    Article  CAS  Google Scholar 

  36. Kuhn, N., Kratz, T., Synthesis of imidazol-2-ylidenes by reduction of imidazole-2(3H)-thiones, Synthesis 1993, 561-562.

    Google Scholar 

  37. Arduengo, A.J. III, Davidson, F., Dias, H.V.R., Goerlich, J.R., Khasnis, D., Marshall, W.J., Prakasha, T.K., An air stable and mixed carbene “dimers”, J. Am. Chem. Soc. 1997, 119:12742-12749.

    Article  CAS  Google Scholar 

  38. Delaude, L., Demonceau, A., Noels, A.F., Visible light induced ring-opening metathesis polymerisation of cyclooctene, Chem. Commun. 2001, 986-987.

    Google Scholar 

  39. Ackermann, L., Bruneau, C., Dixneuf, P.H., Simple new three-component catalytic system for enyne metathesis, Synlett 2001, 397-399.

    Google Scholar 

  40. Sémeril, D., Cléran, M., Bruneau, C., Dixneuf, P.H., New in situ generated ruthenium catalyst for enyne meathesis: access to novel cyclic siloxanes, Adv. Synth. Catal. 2001, 343:184-187.

    Article  Google Scholar 

  41. Zhang, C., Huang, J., Trudell, M.L., Nolan, S.P., Palladium-imidazol-2-ylidene complexes as catalysts for facile and efficient Suzuki cross-coupling reactions of aryl chlorides with arylboronic acids, J. Org. Chem.1999, 64:3804-3805.

    Article  CAS  Google Scholar 

  42. Huang, J., Nolan, S.P., Efficient cross-coupling of aryl chlorides with aryl Grignard reagents (Kumada reaction) mediated by a palladium/imidazolium chloride system, J. Am. Chem. Soc. 1999, 121:9889-9890.

    Article  CAS  Google Scholar 

  43. Grasa, G.A., Nolan, S.P., Palladium/imidazolium salt catalyzed coupling of aryl halides with hypervalent organostannates, Org. Lett. 2001, 3:119-122.

    Article  CAS  Google Scholar 

  44. Viciu, M.S., Grasa, G.A., Nolan, S.P., Catalytic dehalogenation of aryl halides mediated by a palladium/imidazolium salt system, Organometallics 2001, 20:3607-3612.

    Article  CAS  Google Scholar 

  45. Grasa, G.A., Viciu, M.S., Huang, J., Nolan, S.P., Amination reactions of aryl halides with nitrogen-containing reagents mediated by palladium/imidazolium salt systems, J. Org. Chem. 2001, 66:7729-7737.

    Article  CAS  Google Scholar 

  46. Delaude, L., Szypa, M., Demonceau, A., Noels, A.F., New in situ generated ruthenium catalysts bearing N-heterocyclic carbene ligands for the ringopening metathesis polymerization of cyclooctene, Adv. Synth. Catal. 2002, 344:749-756.

    Article  CAS  Google Scholar 

  47. Simal, F., Jan, D., Delaude, L., Demonceau, A., Spirlet, M.-R., Noels, A.F., Evaluation of ruthenium-based complexes for the controlled radical polymerization of vinyl monomers, Can. J. Chem. 2001, 79:529-535.

    Article  CAS  Google Scholar 

  48. Enders, D., Gielen, H., Raabe, G., Runsink, J., Teles, J.H., Diastereoselective synthesis of the first enantiomerically pure (triazolinylidene)ruthenium(II) and -rhodium(III) chelate complexes, Chem. Ber./Recl. 1997, 130:1253-1260.

    Article  CAS  Google Scholar 

  49. Huang, J., Stevens, E.D., Nolan, S.P., Petersen, J.L., Olefin metathesis-active ruthenium complexes bearing a nucleophilic carbene ligand, J. Am. Chem. Soc. 1999, 121:2674-2678.

    Article  CAS  Google Scholar 

  50. Weskamp, T., Schattenmann, W.C., Spiegler, M., Herrmann, W.A., A novel class of  ruthenium catalysts for olefin metathesis, Angew. Chem. Int. Edit. 1998, 37:2490-2493.

    Article  CAS  Google Scholar 

  51. Jan, D., Organometallic engineering of new ruthenium and chromium complexes. Applications to olefin polymerization, Ph.D. thesis, University of Liège (2000).

    Google Scholar 

  52. Hitchcock, P.B., Lappert, M.F., Pye, P.L., Spontaneous N-aryl (rather than P-aryl) orthometallation in the system [RuCl2(PPh3)3(NHC)] (Ar = C6H4Me-4); X-ray crystal and molecular structure of a stereochemically rigid 5-coordi-nate Ru(II) complex, with a short (2.2 A) Ru…H contact, Chem. Commun. 1977, 196-198.

    Google Scholar 

  53. Hitchcock, P.B., Lappert, M.F., Pye, P.L., Thomas, S., Carbene complexes. Part 16. Synthesis and properties of NN′N″N″′-tetra-aryl-substituted electron-rich olefin-derived carbeneruthenium(II) complexes containing a spontane-ously formed ortho-metallated-N-arylcarbene ligand, J. Chem. Soc., Dalton Trans. 1979, 1929-1942.

    Google Scholar 

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Authors and Affiliations

  1. Center for Education and Research on Macromolecules, Institut de Chimie (B6a), University of Liege, Sart-Tilman par, B-4000, Liege, Belgium

    Lionel Delaude & Albert Demonceau

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  1. Lionel Delaude
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  2. Albert Demonceau
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Editors and Affiliations

  1. Hacettepe University, 06800, Beytepe, Ankara, Turkey

    Yavuz Imamoglu

  2. Romanian Academy, Bucharest, Romania

    Valerian Dragutan

  3. Hacettepe University, 06800, Beytepe, Ankara, Turkey

    Solmaz Karabulut

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Delaude, L., Demonceau, A. (2007). Olefin Metathesis With Ruthenium-Arene Catalysts Bearing N-Heterocyclic Carbene Ligands. In: Imamoglu, Y., Dragutan, V., Karabulut, S. (eds) Metathesis Chemistry. NATO Science Series, vol 243. Springer, Dordrecht. https://doi.org/10.1007/978-1-4020-6091-5_14

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