A Mo(VI) Alkylidyne complex with polyhedral oligomeric silsesquioxane ligands: Homogeneous analogue of a silica-supported alkyne metathesis catalyst

Journal of the American Chemical Society

Volumn 128, Issue 46, 2006, Pages 14742-14743

  Hyeon, Mo Cho ^a   Weissman, Haim ^a   Wilson, Scott R ^a   Moore, Jeffrey S ^a  

^a UNIVERSITY OF ILLINOIS AT URBANA CHAMPAIGN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYNE DERIVATIVE; LIGAND; MOLYBDENUM COMPLEX; SILICON DERIVATIVE; SILICON DIOXIDE; SILSESQUIOXANE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CATALYST; CHEMICAL ANALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; RING CLOSING METATHESIS;

EID: 33845229308     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja065101x     Document Type: Article

References (29)

1. Weissman, H.; Plunkett, K. N.; Moore, J. S. Angew. Chem., Int. Ed. 2006, 45, 585.
2. (a) McCullough, L. G.; Schrock, R. R. J. Am. Chem. Soc. 1984, 106, 4067.
3. (b) McCullough, L. G.; Schrock, R. R.; Dewan, J. C.; Murdzek, J. C. J. Am. Chem. Soc. 1985, 107, 5987.
4. (c) Tsai, Y.-C.; Diaconescu, P. L.; Cummins, C. C. Organometattics 2000, 19, 5260.
5. (d) Zhang, W.; Kraft, S.; Moore, J. S. Chem. Commun. 2003, 832.
6. (e) Fürstner, A.; Mathes, C.; Lehmann, C. W. Chem. - Eur. J. 2001, 7, 5299.
7. (f) Chabanas, M.; Baudouin, A.; Copéret, C.; Basset, J.-M. J. Am. Chem. Soc. 2001, 123, 2062.
8. (g) Fürstner, A.; Davis, P. W. Chem. Commun. 2005, 2307.
9. (a) Duchateau, R. Chem. Rev. 2002, 102, 3525.
10. (b) Chandrasekhar, V.; Boomishankar, R.; Nagendran, S. Chem. Rev. 2004, 104, 5847.
11. (c) Abbenhuis, H. C. L. Chem. - Eur. J. 2000, 6, 25.
12. (d) Feher, F. J.; Tajima, T. L. J. Am. Chem. Soc. 1994, 116, 2145.
13. (e) Chabanas, M.; Baudouin, A.; Copéret, C.; Basset, J.-M.; Lukens, W.; Lesage, A.; Hediger, S.; Emsley, L. J. Am. Chem. Soc. 2003, 125, 492.
14. (f) Villemin, D.; Héroux, M.; Blot, V. Tetrahedron Lett. 2001, 42, 3701.
15. (g) Ballard, D. G. H. Adv. Catal. 1973, 23, 263.
16. (h) Solans-Monfort, X.; Clot, E.; Copéret, C.; Eisenstein, O. J. Am. Chem. Soc. 2005, 127, 14015.
17. (a) Wengrovius, J. H.; Sancho, J.; Schrock, R. R. J. Am. Chem. Soc. 1981, 103, 3932.
18. (b) Strutz, H.; Dewan, J. C.; Schrock, R. R. J. Am. Chem. Soc. 1985, 107, 5999.
19. (c) Zhang, W.; Kraft, S.; Moore, J. S. J. Am. Chem. Soc. 2004, 126, 329.
20. (a) Dugas, V.; Chevalier, Y. J. Colloid Interface Sci. 2003, 264, 354.
21. (b) Zhuravlev, L. T. Colloids Surf. A 2000, 173, 1.
22. We saw 1.6-1.7 equiv of free aniline by NMR when we added silica treated at 400°C to complex 1. The monosiloxy complex is likely to be present, but we cannot fully account for the observed additional 0.6-0.7 equiv of free aniline without considering additional ligand displacement.
23. Why catalysts from D and T cause polymerization while M does not remains open to speculation. The bite angle for bidentate or tridentate ligands is certainly smaller than the coordination angle by monodentate ligands. As a result, the space opposite of the chelating ligand, where the alkyne substrate approaches, is expanded. In this scenario, the alkyne substrate might insert repeatedly into the Mo-C bond to give polymers.
24. Shih, K.-Y.; Schrock, R. R.; Kempe, R. J. Am. Chem. Soc. 1994, 116, 8804.
25. Tsai and co-workers reported the X-ray structure of a tetracoordinated molybdenum alkylidyne complex with three alkoxy ligands in which a free aniline did not interact with the Mo center. See ref 2c.
26. Similarly, Schrock suggested that a two-electron donor could block metathesis by binding strongly to the metal to give a five-coordinated species. See: Schrock, R. R. Polyhedron 1995, 14, 3177.
27. tBu groups changed from 6.300 to 6.319 ppm and from 1.177 to 1.170 ppm, respectively. This fact partially supports the idea that the additional 3 equiv of M in the solution weaken the interaction between Mo and aniline.
28. Zhang, W.; Moore, J. S. J. Am. Chem. Soc. 2004, 126, 12796.
29. Brizius, G.; Bunz, U. H. F. Org. Lett. 2002, 4, 2829.