Hetero-bimetallic complexes of titanatranes with aluminum alkyls: Synthesis, structural analysis, and their use in catalysis for ethylene polymerization

Organometallics

Volumn 29, Issue 16, 2010, Pages 3500-3506

  Gurubasavaraj, Prabhuodeyara M ^a   Nomura, Kotohiro ^a,b  

^a NARA INSTITUTE OF SCIENCE AND TECHNOLOGY   (Japan)

^b TOKYO METROPOLITAN UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

AL COMPLEX; ALUMINUM ALKYLS; AMINE LIGAND; BIMETALLIC COMPLEXES; CATALYTIC ACTIVITY; CATIONIC SPECIES; CO CATALYSTS; CRYSTALLOGRAPHIC ANALYSIS; ETHYLENE POLYMERIZATION; HIGH-MOLECULAR WEIGHT POLYMERS; METHYLALUMINOXANE; OCTAHEDRAL GEOMETRY; TETRAHEDRAL GEOMETRY; TI-O BONDS; UNIFORM DISTRIBUTION;

ALUMINUM; CATALYSIS; CATALYST ACTIVITY; DYES; ETHYLENE; POLYMERIZATION; POLYMERS; SINGLE CRYSTALS; STRUCTURAL ANALYSIS; TOLUENE;

TITANIUM COMPOUNDS;

EID: 77955693377     PISSN: 02767333     EISSN: 15206041     Source Type: Journal    
DOI: 10.1021/om100119g     Document Type: Article

References (63)

1. For selected reviews/accounts, see: Britovsek, G. J. P.; Gibson, V. C.; Wass, D. F. Angew. Chem., Int. Ed. 1999, 38, 428
2. McKnight, A. L.; Waymouth, R. M. Chem. Rev. 1998, 98, 2587
3. Kaminsky, W.; Arndt, M. Adv. Polym. Sci. 1997, 127, 144
4. Bochmann, M. J. Chem. Soc., Dalton Trans. 1996, 255
5. Marks, T. J. Acc. Chem. Res. 1992, 25, 57
6. Jordan, R. F. Adv. Organomet. Chem. 1991, 32, 325
7. Kaminsky, W., Ed. Metalorganic Catalysts for Synthesis and Polymerization: Recent Results by Ziegler-Natta and Metallocene Investigations; Springer-Verlag: Berlin, 1999.
8. Chen, E. Y-X.; Marks, T. J. Chem. Rev. 2000, 100, 1391
9. Boor, J., Jr. Ziegler-Natta Catalysts and Polymerizations; Academic Press: New York, 1979.
10. Chien, J. C. W., Ed. Coordination Polymerization; Academic Press: New York, 1975.
11. Andresen, A.; Cordes, H. G.; Herwig, H.; Kaminsky, W.; Merk, A.; Mottweiler, R.; Pein, J.; Sinn, H.; Vollmer, H. J. Angew. Chem., Int. Ed. Engl. 1976, 15, 630
12. Sinn, H.; Kaminsky, W.; Vollmer, H.-J.; Woldt, R. Angew. Chem., Int. Ed. Engl. 1980, 19, 390
13. Sinn, H.; Kaminsky, W. Adv. Organomet. Chem. 1980, 18, 99
14. Recent review article: The Chemistry of Catalyst Activation: The Case of Group 4 Polymerization Catalyst. Bochmann, M. Organometallics 2010, in press (web released on June 29, DOI: 10.1021/om1004447). Related references are cited therein.
15. 3 adducts), (4) see: Bochmann, M.; Lancaster, J. J. Angew. Chem., Int. Ed. Engl. 1994, 33, 1634
16. Petros, R. A.; Norton, J. R. Organometallics 2004, 23, 5105
17. Schröder, L.; Brintzinger, H. H.; Babushkin, D. E.; Fischer, D.; Mülhaupt, R. Organometallics 2005, 24, 867
18. Bryliakov, K. P.; Babushkin, D. E.; Talsi, E. P.; Voskoboynikov, A. Z.; Gritzo, H.; Schröder, L.; Damrau, H. R. H.; Wieser, U.; Schaper, F.; Brintzinger, H. H. Organometallics 2005, 24, 894
19. Bolton, P. D.; Clot, E.; Cowley, A. R.; Mountford, P. Chem. Commun. 2005, 3313
20. Bolton, P. D.; Clot, E.; Cowley, A. R.; Mountford, P. J. Am. Chem. Soc. 2006, 128, 15005
21. Janas, Z.; Jerzykiewicz, L. B.; Sobota, P.; Szczegot, K.; Wiceniewska, D. Organometallics 2005, 24, 3987
22. Fandos, R.; Gallego, B.; Otero, A.; Rodriguez, A.; Ruiz, M. J.; Terreros, P.; Pastor, C. Organometallics 2007, 26, 2896
23. Gurubasavaraj, P. M.; Mandal, S. K.; Roesky, H. W.; Oswald, R. B.; Pal, A.; Noltemeyer, M. Inorg. Chem. 2007, 46, 1056
24. Gurubasavaraj, P. M.; Roesky, H. W.; Mandal, S. K.; Oswald, R. B.; Pal, A.; Herbst-Irmer, R. Inorg. Chem. 2008, 47, 5324
25. Verkade, J. G. Acc. Chem. Res. 1993, 26, 483
26. Verkade, J. G. Cood. Chem. Rev. 1994, 137, 233
27. Gueta-Neyroud, T.; Tumanskii, B.; Kapon, M.; Eisen, M. S. Macromolecules 2007, 40, 5261
28. Allcock, H. R.; Patterson, D. B.; Evans, T. L. Macromolecules 1979, 12, 172
29. Phomphrai, K.; Fenwick, A. E.; Sharma, S.; Fanwick, P. E.; Caruthers, J. M.; Delgass, W. N.; Abu-Omar, M. M.; Rothwell, I. P. Organometallics 2006, 25, 241
30. Michalczyk, L.; Gala, S. de.; Bruno, J. W. Organometallics 2001, 20, 5547
31. Dang, Y. Coord. Chem. Rev. 1994, 135, 93
32. Some examples on atrane ligand based complexes: Voronkov, M. G.; Dyakov, V. M.; Kirpichenko, S. V. J. Organomet. Chem. 1982, 233, l
33. Schrock, R. R. Acc. Chem. Res. 1997, 30, 9-16
34. Gade, L. H. Chem. Commun. 2000, 173
35. Nugent, W. A. J. Am. Chem. Soc. 1992, 114, 2768
36. Nugent, W. A.; Harlow, R. L. J. Am. Chem. Soc. 1994, 116, 6142
37. Furia, F. D.; Licini, G.; Modena, G.; Motterle, R.; Nugent, W. A. J. Org. Chem. 1996, 61, 5175
38. Bonchio, M.; Calloni, S.; Furia, F. D.; Licini, G.; Modena, G.; Moro, S.; Nugent, W. A. J. Am. Chem. Soc. 1997, 119, 6935
39. Nugent, W. A. J. Am. Chem. Soc. 1998, 120, 7139
40. Bonchio, M.; Licini, G.; Modena, G.; Bortolini, O.; Moro, S.; Nugent, W. A. J. Am. Chem. Soc. 1999, 121, 6258
41. Kim, Y.; Hong, E.; Lee, M. H.; Kim, J.; Han, Y.; Do, Y. Organometallics 1999, 18, 36
42. Kim, Y.; Han, Y.; Hwang, J.-W.; Kim, M. W.; Do, Y. Organometallics 2002, 21, 1127
43. Kim, Y.; Do, Y. J. Organomet. Chem. 2002, 655, 186
44. Lee, K.-S.; Kim, Y.; Ihm, S.-K.; Do, Y.; Lee, S. J. Organomet. Chem. 2006, 691, 1121
45. Lee, J.; Hong, Y.; Kim, J. H.; Kim, S. H.; Do, Y.; Shin, Y. K.; Kim, Y. J. Organomet. Chem. 2008, 693, 3715
46. Wang, W.; Fujiki, M.; Nomura, K. Macromol. Rapid Commun. 2004, 25, 504
47. Padmanabhan, S.; Katao, S.; Nomura, K. Organometallics 2007, 26, 1616
48. Padmanabhan, S.; Wnag, W; Katao, S.; Nomura, K. Macromol. Symp. 2007, 260, 133
49. Gurubasavaraj, P. M.; Nomura, K. Inorg. Chem. 2009, 48, 9491
50. Report concerning ethylene/1-hexene polymerization using titanium complexes containing tris(alkoxo)amine ligands: Sudhakar, P.; Amburose, C. V.; Sundararajan, G.; Nethaji, M. Organometallics 2004, 23, 4462
51. Sudhakar, P.; Sundararajan, G. Macromol. Rapid Commun. 2005, 26, 1854
52. 1H NMR spectra measured at various temperatures are shown in the Supporting Information.
53. Structural analysis results including a table summarizing crystallographic data and collection parameters of complexes 3a, 3b, and 4a, structure reports, and CIF files are shown in the Supporting Information. Complex 4a showed a mixture of two complexes that possessed similar bond distances and angles. Toluene molecules that could not be defined were also observed as disordered molecules (reason for the level A errors in the check CIF file). Details are shown in the Supporting Information.
54. Kol, M.; Shamis, M.; Goldberg, I.; Goldschmidt, Z.; Alfi, S.; Hayut-Salant, E. Inorg. Chem. Commun. 2001, 4, 177
55. We could not conduct the ethylene polymerization in n-octane because these complexes (3a, b and 4a) showed low solubility in n-octane, although the activities of 1 and 2 in n-octane were higher than those in toluene. (11a)
56. One probable reason we may take into consideration is that these polymerizations were conducted not in octane, as in the previous report, (11a) but in toluene, which may coordinate to Ti. Coordination of toluene in the proposed catalytically active species, for examples: Scollard, J. D.; McConville, D. H.; Payne, N. C.; Vittal, J. J. Macromolecules 1996, 29, 5241
57. A reviewer commented that we should consider the reason that the activities of 3b were low. The activities of 3a, b with high Al/Ti molar ratio (Al/Ti = 3000) at 120 °C were close, probably due to alkyl exchange under these conditions. A reviewer suggested fast reduction to Ti(III) by 3b, but we do not have firm results for explaining the experimental observations. We recently conducted alkene/alkyne insertion chemistry of these alkyl complexes: Saeed, I.; Nomura, K. Unpublished results, manuscript in preparation.
58. The resultant polymers possessed rather broad but unimodal molecular weight distributions probably because the resultant polymers were insoluble owing to their ultrahigh molecular weights (heterogeneous nature in the reaction mixture).
59. 1H NMR spectra, we have never observed the actual catalytically active species or zwitterionic species (by NMR spectra). The role of MAO to improve the activity also seems obvious (the activity of 4a in the presence of MAO was much higher than that without MAO), and we need to explain the role in this catalysis (maybe effective for dissociation of the Ti-O arm to generate the active species or shift the equilibrium between dormant and active species). The related chemistry is under investigation.
60. DIRDIF94: Beurskens, P. T.; Admiraal, G.; Beurskens, G.; Bosman, W. P.; de Delder, R.; Israel, R.; Smits, J. M. M. The DIRDIF94 Program System, Technical Report of Crystallography Laboratory; University of Nijmegen: The Netherlands, 1994.
61. Crystal Structure 3.8, Crystal Structure Analysis Package; Rigaku and Rigaku/MSC: The Woodlands TX, 2000-2007.
62. Carruthers, J. R.; Rollett, J. S.; Betteridge, P. W.; Kinna, D.; Pearce, L.; Larsen, A.; Gabe, E. CRYSTALS Issue 11; Chemical Crystallography Laboratory: Oxford, UK, 1999.
63. Sheldrick, G. M. SHELX97; Bruker AXS: Madison, WI, 1997.