Structure and activity peculiarities of ruthenium quinoline and quinoxaline complexes: Novel metathesis catalysts

Organometallics

Volumn 25, Issue 15, 2006, Pages 3599-3604

  Barbasiewicz, Michał ^a   Szadkowska, Anna ^a   Bujok, Robert ^a   Grela, Karol ^a  

^a INSTITUTE OF ORGANIC CHEMISTRY   (Poland)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSTS; COMPLEXATION; ISOMERIZATION; MOLECULAR STRUCTURE; NITROGEN COMPOUNDS; SYNTHESIS (CHEMICAL); THERMODYNAMICS;

5-VINYLQUINOXALINE; CIS-DICHLORO ISOMERS; GRUBBS-TYPE COMPLEXES; METATHESIS CATALYSTS;

RUTHENIUM COMPOUNDS;

EID: 33746410595     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om060091u     Document Type: Article

References (51)

1. Handbook of Metathesis; Grubbs, K. H., Ed.; Wiley-VCH: Weinheim, Germany, 2003; Vols. 1-3.
2. Ung, T.; Hejl, A.; Grubbs, R. H.; Schrodi, Y. Organometallics 2004, 23, 5399.
3. Slugovc, C.; Burtscher, D.; Stelzer, F.; Mereiter, K. Organometallics 2005, 24, 2255.
4. (a) Harrity, J. P. A.; La, D. S.; Cefalo, D. R.; Visser, M. S.; Hoveyda, A. H. J. Am. Chem. Soc. 1998, 120, 2343.
5. (b) Kingsbury, J. S.; Harrity, J. P. A.; Bonitatebus, P. J., Jr.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 791.
6. (c) Garber, S. B.; Kingsbury, J. S.; Gray, B. L.; Hoveyda, A. H. J. Am. Chem. Soc. 2000, 122, 8168.
7. (a) Grela, K.; Harutyunyan, S.; Michrowska, A. Angew. Chem. 2002, 114, 4210;
8. Angew. Chem., Int. Ed. 2002, 41, 4038.
9. (b) Harutyunyan, S.; Michrowska, A.; Grela, K. A Highly Active Ruthenium (Pre)catalyst for Metathesis Reactions. In Catalysts for Fine Chemical Synthesis; Roberts, S. M., Whittall, J., Mather, P., McCormack, P.; Eds.; Wiley: New York, 2004; Vol. 3 (Metal Catalysed Carbon-Carbon Bond-Forming Reactions), Chapter 9.1, pp 169-173.
10. (c) Gulajski, L; Michrowska, A.; Bujok, R.; Grela, K. J. Mol Catal. A: Chem., in press.
11. Michrowska, A.; Bujok, R.; Harutyunyan, S.; Sashuk, V.; Dolgonos, G.; Grela, K. J. Am. Chem. Soc. 2004, 126, 9318.
12. Fürstner, A.; Thiel, O. R.; Lehmann, C. W. Organometallics 2002, 21, 331.
13. For some earlier examples of cis-dichloride complexes, see: Trnka, T. M. ; Day, M. W.; Grubbs, R. H. Organometallics 2001, 20, 3845 and references therein.
14. Slugovc, C.; Perner, B.; Stelzer, F.; Mereiter, K. Organometallics 2004, 23, 3622.
15. For similar trans to cis rearrangements of nonchelating ligands on silica gel, see: Prühs, S.; Lehmann, C. W.; Fürstner, A. Organometallics 2004, 23, 280.
16. (a) For complexes bearing chelating pyridinyl-alcoholato ligands, see: Denk, K.; Fridgen, J.; Herrmann, W. A. Adv. Synth. Catal. 2002, 344, 666.
17. (b) Cationic and neutral ruthenium vinylidene complexes containing tridentate pyridine ligands: Del Rio, R.; Van Koten, G. Tetrahedron Lett. 1999, 40, 1401.
18. (c) For neutral and cationic Ru tris(pyrazolyl)borate alkylidene and vinylidene complexes, see: Sanford, M. S.; Henling, L. M.; Orubbs, R. H. Organometallics 1998,17, 5384.
19. (d) Katayama, H.; Yoshida, T.; Osawa, F. J. Organomet. Chem. 1998, 52, 203.
20. van der Schaaf, P. A.; Kolly, R.; Kirner, H.-J.; Rime, F.; Mühlebach, A.; Hafner, A. J. Organomet. Chem. 2000, 606, 65.
21. For other Ru complexes, containing Schiff base ligands, see: (a) Chang, S.; Jones, L.-R., II.; Wang, C.; Henling, L. M.; Grubbs, R. H. Organometallics 1998,17, 3460.
22. (b) De Clercq, B.; Verpoort, F. Adv. Synth. Catal. 2002, 344, 639.
23. (c) De Clercq, B.; Verpoort, F. J. Mol. Catal. A: Chem. 2002, 180, 67.
24. (d) Opstal, T.; Verpoort, F. Angew. Chem., Int. Ed. 2003, 42, 2876.
25. (e) Opstal, T.; Verpoort, F. Synlett 2002, 935.
26. (f) De Clercq, B.; Lefebvre, F.; Verpoort, F. Appl. Catal. A: Gen. 2003, 247.
27. (g) De Clercq, B.; Lefebvre, F.; Verpoort, F. New J. Chem. 2002, 26, 1201.
28. The PhCH=NPh motif within the catalyst structure, described in ref 3, was twisted by about 30° for the five-membered-ring chelate complex.
29. (a) Stille, J. K.; Echavarren, A. M. J. Am. Chem. Soc. 1987, 109, 5478.
30. (b) 8-Quinolinyl triflate is commercially available from Aldrich Inc.
31. The reaction was performed according to the procedure described in: Crisp, G. T.; Papadopoulos, S. Aust. J. Chem. 1989, 42, 279.
32. Brown, W. D.; Gouliaev, A. H. Synthesis 2002, 83.
33. The reaction was performed according to the procedure described in: van Mullekom, H. A. M.; Vekemans, J. A. J. M.; Meijer, E. W. Chem. Eur. J. 1998, 4, 1235.
34. 1H NMR spectra of similar isomeric complexes see ref 2.
35. We wish to acknowledge for use of a free version of Ortep-3 for Windows program: Farrugia, L. J. J. Appl. Crystallogr. 1997, 30, 565.
36. 2): δ 17.13 (1a), 17.47 (1b), 17.02 (2a), 17.29 ppm (2b).
37. Benitez, D.; Goddard, W. A. J. Am. Chem. Soc. 2005, 127, 12218.
38. 2 gave no detectable Ru=CH NMR signal for la (17.13 ppm), even on prolonged equilibration.
39. A similar rationalization was presented in ref 2.
40. Frisch, M. J.; Trucks, O. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Kiene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03, revision B.05; Gaussian, Inc.: Wallingford, CT, 2004.
41. All of the calculations were performed using Gaussian 03. The structures of 8-vinylquinoline and 5-vinylquinoxaline were optimized using B3LYP with the 6-31G** basis set in the gas phase. Only real values of the analytical harmonic vibrational frequencies confirmed that the geometries under study correspond to the minimum-energy structures.
42. 2O at 25°C: Boraei, A. A. A. Monatsh. Chem. 1994, 125, 869.
43. 2O at 25 °C: King, J. F.; Hillhouse, J. H.; Skonieczny, S. Can. J. Chem. 1984, 62, 1977.
44. 2O at 25°C: Goethals, M.; Czarnik-Matusewicz, B.; Zeegers-Huyskents, T. J. Heterocycl. Chem. 1999, 36, 49.
45. Electron density cubes from total SCF density (isoval = 0.0004; mapped with ESP) were generated with: GaussView 3.0; Gaussian, Inc., Wallingford, CT (www.gaussian.com).
46. The magnitude of the observed effect of carbon-to-nitrogen substitution on isomerization and metathesis processes seems to be relatively small, as compared to, for example, differences of Brønsted basicities of chelating nitrogen atoms in ligands (the difference in ligand properties exhibits a bit more pronounced effect on the rate of isomerization in this case). However, the limited data impeded us from speculating on deeper mechanistic reasons for this observation (however, for some structural considerations, see ref 31). We wish to thank a reviewer for drawing our attention to this issue.
47. 22 in the gas phase the cis isomer of a similar complex is less stable than the trans isomer, due to the unfavorable dipole moment arising from polarized Ru-Cl bonds (in the trans complex the dipole moments of Ru-Cl bonds mutually cancel). However, this effect is dimished by solvents with high dielectric constant, e.g. dichloromethane, where the cis form predominates in an equilibrium. The presence of the second nitrogen atom in the quinoxaline ring in 2b creates a dipole moment that is opposite to that of the equatorial chloride ion and, thus, partially reduces the total polarity of this complex. In fact, although 2b should be slightly better stabilized as compared to Ib, it is formed at a significantly lower rate.
48. For the postulated π-face interactions in Ru carbene complexes containing NHC ligands, see: (a) Fürstner, A.; Ackermann, L.; Gabor, B.; Goddard, R.; Lehmann, C. W.; Mynott, R.; Stelzer, F.; Thiel, O. R. Chem. Eur. J. 2001, 7, 3236.
49. (b) Süssner, M.; Plenio, H. Chem. Commun. 2005, 5417.
50. In this context it is necessary to presume that the tested substrates do not activate the catalysts or activate them to a similar extent.
51. Part of this work has been presented as a poster: Szadkowska, A.; Barbasiewicz, M.; Grela, K. Synthesis and application of new latent ruthenium carbene catalysts. European Congress of Young Chemists "YoungChem 2005", Rydzyna, Poland, October 12-16, 2005.