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

  • Lionel Delaude
  • Albert Demonceau
Conference paper
Part of the NATO Science Series book 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.

Keywords

Triazole Phosphine Rhodium MeCN Chlorobenzene 

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References

  1. [1]
    Le Bozec, H., Touchard, D., Dixneuf, P.H., Organometallic chemistry of arene ruthenium and osmium complexes, Adv. Organomet. Chem. 1989, 29:163-247.CrossRefGoogle Scholar
  2. [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.CrossRefGoogle Scholar
  3. [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.CrossRefGoogle Scholar
  4. [4]
    Rigby, J.H., Kondratenko, M.A., Arene complexes as catalysts, Top. Organonomet. Chem. 2004, 7:181-204.Google Scholar
  5. [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.CrossRefGoogle Scholar
  6. [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.CrossRefGoogle Scholar
  7. [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.CrossRefGoogle Scholar
  8. [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.CrossRefGoogle Scholar
  9. [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.CrossRefGoogle Scholar
  10. [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.CrossRefGoogle Scholar
  11. [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.CrossRefGoogle Scholar
  12. [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.CrossRefGoogle Scholar
  13. [13]
    Fürstner, A., Ackermann, L., A most user-friendly protocol for ring closing metathesis reactions, Chem. Commun. 1999, 95-96.Google Scholar
  14. [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.CrossRefGoogle Scholar
  15. [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. [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.CrossRefGoogle Scholar
  17. [17]
    Arduengo, A.J. III, Harlow, R.L., Kline, M., A stable crystalline carbene, J. Am. Chem. Soc. 1991, 113:361-363.CrossRefGoogle Scholar
  18. [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.CrossRefGoogle Scholar
  19. [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.CrossRefGoogle Scholar
  20. [20]
    Arduengo, A.J. III, Looking for stable carbenes: the difficulty in starting anew, Acc. Chem. Res. 1999, 32:913-921.CrossRefGoogle Scholar
  21. [21]
    Bourrisou, D., Guerret, O., Gabbaï, F.P., Bertrand, G., Stable carbenes, Chem. Rev. 2000, 100:39-91.Google Scholar
  22. [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.CrossRefGoogle Scholar
  23. [23]
    Herrmann, W.A., Weskamp, T., Böhm, V.P.W., Metal complexes of stable carbenes, Adv. Organomet. Chem. 2002, 48:1-69.CrossRefGoogle Scholar
  24. [24]
    Herrmann, W.A., N-heterocyclic carbenes: a new concept in organometallic catalysis, Angew. Chem. Int. Edit. 2002, 41:1290-1309.CrossRefGoogle Scholar
  25. [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. [26]
    Nair, V., Bindu, S., Sreekumar, V., N-heterocyclic carbenes: reagents, not just ligands!, Angew. Chem. Int. Edit. 2004, 43:5130-5135.CrossRefGoogle Scholar
  27. [27]
    Enders, D., Balensiefer, T., Nucleophilic carbenes in asymmetric organocatalysis, Acc. Chem. Res. 2004, 37:534-541.CrossRefGoogle Scholar
  28. [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.CrossRefGoogle Scholar
  29. [29]
    Herrmann, W.A., Köcher, C., N-heterocyclic carbenes, Angew. Chem. Int. Edit. 1997, 36:2162-2187.CrossRefGoogle Scholar
  30. [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.CrossRefGoogle Scholar
  31. [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. [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.CrossRefGoogle Scholar
  33. [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. CrossRefGoogle Scholar
  34. [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.CrossRefGoogle Scholar
  35. [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.CrossRefGoogle Scholar
  36. [36]
    Kuhn, N., Kratz, T., Synthesis of imidazol-2-ylidenes by reduction of imidazole-2(3H)-thiones, Synthesis 1993, 561-562.Google Scholar
  37. [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.CrossRefGoogle Scholar
  38. [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. [39]
    Ackermann, L., Bruneau, C., Dixneuf, P.H., Simple new three-component catalytic system for enyne metathesis, Synlett 2001, 397-399.Google Scholar
  40. [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.CrossRefGoogle Scholar
  41. [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.CrossRefGoogle Scholar
  42. [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.CrossRefGoogle Scholar
  43. [43]
    Grasa, G.A., Nolan, S.P., Palladium/imidazolium salt catalyzed coupling of aryl halides with hypervalent organostannates, Org. Lett. 2001, 3:119-122.CrossRefGoogle Scholar
  44. [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.CrossRefGoogle Scholar
  45. [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.CrossRefGoogle Scholar
  46. [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.CrossRefGoogle Scholar
  47. [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.CrossRefGoogle Scholar
  48. [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.CrossRefGoogle Scholar
  49. [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.CrossRefGoogle Scholar
  50. [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.CrossRefGoogle Scholar
  51. [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. [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. [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

Copyright information

© Springer 2007

Authors and Affiliations

  • Lionel Delaude
    • 1
  • Albert Demonceau
    • 1
  1. 1.Center for Education and Research on MacromoleculesInstitut de Chimie (B6a), University of LiegeBelgium

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