Study of homogeneously catalyzed Ziegler-Natta polymerization of ethene by ESI-MS

Angewandte Chemie - International Edition

Volumn 45, Issue 6, 2006, Pages 977-981

  Santos, Leonardo Silva ^a   Metzger, Jürgen O ^a  

^a UNIVERSITY OF OLDENBURG   (Germany)

Author keywords

Homogeneous catalysis; Mass spectrometry; Microreactors; Polymerization; Reaction mechanisms

Indexed keywords

CATALYSIS; CATALYST ACTIVITY; MASS SPECTROMETRY; POLYMERIZATION; REACTION KINETICS;

CATIONIC INTERMEDIATES; ESI MASS SPECTROMETER; MICROREACTORS;

OLEFINS;

EID: 32044437434     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200503307     Document Type: Article

References (61)

1. A. Andresen, H. G. Cordes, H. Herwig, W. Kaminsky, A. Merk, R. Mottweiler, J. Pein, H. Sinn, H. J. Vollmer, Angew. Chem. 1976, 88, 689-690;
2. Angew. Chem. Int. Ed. Engl. 1976, 15, 630-632.
3. a) H. Sinn, W. Kaminsky, Adv. Organomet. Chem. 1980, 18, 99-149;
4. b) H. Sinn, W. Kaminsky, H.-J. Vollmer, R. Woldt, Angew. Chem. 1980, 92, 396-402;
5. Angew. Chem. Int. Ed. Engl. 1980, 19, 390-392.
6. a) W. Kaminsky, R. Steiger, Polyhedron 1988, 7, 2375-2381;
7. b) D. Cam, U. Giannini, Makromol. Chem. 1992, 193, 1049-1055.
8. a) XPS: P. G. Gassman, M. R. Callstrom, J. Am. Chem. Soc. 1987, 109, 7875-7876;
9. 13C NMR: C. Sishta, R. M. Hathorn, T. J. Marks, J. Am. Chem. Soc. 1992, 114, 1112-1114.
10. a) A. R. Siedle, W. M. Lamanna, R. A. Newmark, J. N. Schroepfer, J. Mol. Catal. A 1998, 128, 257-271;
11. b) I. Tritto, S. X. Li, M. C. Sacchi, P. Locatelli, G. Zannoni, Macromolecules 1995, 28, 5358-5362;
12. c) I. Tritto, S. Li, M. C. Sacchi, G. Zannoni, Macromolecules 1993, 26, 7111-7115.
13. a) W. Kaminsky, Macromol. Chem. Phys. 1996, 197, 3907-3945;
14. b) W. Kaminsky, C. Strubel, J. Mol. Catal. A 1998, 128, 191-200.
15. a) D. Coevoet, H. Cramail, A. Deffieux, Macromol. Chem. Phys. 1999, 200, 1208-1214;
16. b) J.-N. Pédeutour, D. Coevoet, H. Cramail, A. Deffieux, Macromol. Chem. Phys. 1999, 200, 1215-1221;
17. c) D. E. Babushkin, N. V. Semikolenova, V. A. Zakharov, E. P. Talsi, Macromol. Chem. Phys. 2000, 201, 558-567.
18. L. S. Santos, L. Knaack, J. O. Metzger, Int. J. Mass Spectrom. 2005, 246, 84-104.
19. a) J. Griep-Raming, S. Meyer, T. Bruhn, J. O. Metzger, Angew. Chem. 2002, 114, 2863-2866;
20. Angew. Chem. Int. Ed. 2002, 41, 2738-2742;
21. b) S. Meyer, R. Koch, J. O. Metzger, Angew. Chem. 2003, 115, 4848-4851;
22. Angew. Chem. Int. Ed. 2003, 42, 4700-4703.
23. a) L. S. Santos, C. H. Pavam, W. P. Almeida, F. Coelho, M. N. Eberlin, Angew. Chem. 2004, 116, 4430-4433;
24. Angew. Chem. Int. Ed. 2004, 43, 4330-4333;
25. b) J. B. Domingos, E. Longhinotti, T. A. S. Brandao, C. A. Bunton, L. S. Santos, M. N. Eberlin, F. Nome, J. Org. Chem. 2004, 69, 6024-6033;
26. c) E. C. Meurer, L. S. Santos, R. A. Pilli, M. N. Eberlin, Org. Lett. 2003, 5, 1391-1394;
27. d) A. A. Sabino, A. H. L. Machado, C. R. D. Correia, M. N. Eberlin, Angew. Chem. 2004, 116, 2568-2572;
28. Angew. Chem. Int. Ed. 2004, 43, 2514-2518.
29. a) C. Hilderling, C. Adlhart, P. Chen, Angew. Chem. 1998, 110, 2831-2835;
30. Angew. Chem. Int. Ed. 1998, 37, 2685-2689;
31. b) P. Chen, Angew. Chem. 2003, 115, 2938-2954;
32. Angew. Chem. Int. Ed. 2003, 42, 2832-2847;
33. c) C. Raminelli, M. H. G. Prechtl, L. S. Santos, M. N. Eberlin, J. V. Comasseto, Organometallics 2004, 23, 3990-3996.
34. D. Feichtinger, D. A. Plattner, P. Chen, J. Am. Chem. Soc. 1998, 120, 7125-7126.
35. a) X. M. Yang, C. L. Stern, T. J. Marks, J. Am. Chem. Soc. 1994, 116, 10 015-10 031;
36. b) M. Bochmann, S. J. Lancaster, Angew. Chem. 1994, 106, 1715-1718;
37. Angew. Chem. Int. Ed. Engl. 1994, 33, 1634-1637;
38. c) L. Jia, X. M. Yang, A. Ishihara, T. J. Marks, Organometallics 1995, 14, 3135-3137.]
39. a) C. M. Whitehouse, R. N. Dreyer, M. Yamashita, J. B. Fenn, Anal. Chem. 1985, 57, 675-679;
40. b) J. B. Fenn, M. Mann, C. K. Meng, S. F. Wong, C. M. Whitehouse, Science 1989, 246, 64-71;
41. c) R. B. Cole, Electrospray Ionization Mass Spectroscopy, Wiley, New York, 1997.
42. F. C. Gozzo, L. S. Santos, R. Augusti, C. S. Consorti, J. Dupont, M. N. Eberlin, Chem. Eur. J. 2004, 10, 6187-6193.
43. W. Kaminsky, K. Kulper, H. H. Brintzinger, F. R. W. P. Wild, Angew. Chem. 1985, 97, 507-508;
44. Angew. Chem. Int. Ed. Engl. 1985, 24, 507-508.
45. -1. By connecting the microreactor directly to the spray capillary, reaction times from 0.3 to 28 s could be covered.
46. -1 by means of a microsyringe pump. MS/MS experiments were carried out by mass selection of a specific ion in Q1 which was then submitted to collision-induced dissociation (CID) with argon in the collision chamber. The product-ion MS analysis was accomplished with the high-resolution orthogonal TOF analyzer.
47. 96Zr (2.80 %) - the Zr-containing species were be mass detected as clusters of isotopologous ions.
48. Similar CID behavior was described in Ref. [12] and by C. S. Christ, Jr., J. R. Eyler, D. E. Richardson, J. Am. Chem. Soc. 1990, 112, 596-607.
49. [12] reported that high voltages were necessary to fragment similar clusters obtained through borates, we observed ready release of MeCN.
50. + (Y. W. Alelyunas, R. F. Jordan, S. F. Echols, S. L. Borkowsky, P. K. Bradley, Organometallics 1991, 10, 1406-1416). We performed the same reaction as described by Jordan but employed MAO as co-catalyst, and even after 48 h no product arising from reaction of 5 and MeCN was observed by CID experiments.
51. The T-wave collision cell in the Q-TOF Premier used, enabled us to observe several product ions: K. Giles, S. D. Pringle, K. R. Worthington, D. Little, J. L. Wildgoose, R. H. Bateman, Rapid Commun. Mass Spectrom. 2004, 18, 2401-2414.
52. -2 mbar. For uses of QqTOFs, see: I. V. Chernushevich, A. V. Loboda, B. A. Thomson, J. Mass Spectrom. 2001, 36, 849-865.
53. The product-ion mass spectrum was acquired under multiple-collision conditions that caused typical beam attenuations of 50-70 % in the collision cell so as to increase the reaction yields and to promote the collisional quenching of both the reactant and product ions. Reactant ions should therefore display no or negligible amounts of excess internal energy. For similar studies in ion/molecule reactions, see: A. E. P. M. Sorrilha, L. S. Santos, F. C. Gozzo, R. Sparrapan, R. Augusti, M. N. Eberlin, J. Phys. Chem. A 2004, 108, 7009-7020, and references therein.
54. 4 molecule insertions (n = 1-4) in good yields.
55. P. Watson, D. C. Roe, J. Am. Chem. Soc. 1982, 104, 6471-6473;
56. J. E. Bercaw, D. L. Davia, P. T. Wolczanski, Organometallics 1986, 5, 443-450.
57. 2 = 5 cm.
58. a) R. F. Jordan, W. E. Dasher, S. F. Echols, J. Am. Chem. Soc. 1986, 108, 1718-1719;
59. b) R. F. Jordan, C. S. Bajgur, R. Willett, B. Scott, J. Am. Chem. Soc. 1986, 108, 7410-7411.
60. 2), which brings the reaction solution after MeCN dilution to ESI ion source, did not affect the relative intensities of the observed ions (Figure 1, bottom right).
61. D. B. Jacobson, B. S. Freiser, J. Am. Chem. Soc. 1983, 105, 736-742.