A fully integrated high-throughput screening methodology for the discovery of new polyolefin catalysts: Discovery of a new class of high temperature single-site group (IV) copolymerization catalysts

Journal of the American Chemical Society

Volumn 125, Issue 14, 2003, Pages 4306-4317

  Boussie, Thomas R ^a,d   Diamond, Gary M ^a,d   Goh, Christopher ^a,d   Hall, Keith A ^a,d   LaPointe, Anne M ^a,d   Leclerc, Margarete ^a,d   Lund, Cheryl ^a,d   Murphy, Vince ^a,d   Shoemaker, James A W ^a,d   Tracht, Ursula ^b   Turner, Howard ^a,d   Zhang, Jessica ^a,d   Uno, Tetsuo ^c   Rosen, Robert K ^a   Stevens, James C ^a  

^a DOW CHEMICAL COMPANY   (United States)

^b BAYER AG   (Germany)

^c GENOMICS INSTITUTE OF THE NOVARTIS RESEARCH FOUNDATION   (United States)

^d SYMYX TECHNOLOGIES   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

SECONDARY SCREENING;

COMPLEXATION; HIGH TEMPERATURE EFFECTS; MOLECULAR STRUCTURE; POLYOLEFINS;

CATALYSTS;

AMIDE; ETHER; HAFNIUM; METAL COMPLEX; POLYMER; POLYOLEFIN;

ARTICLE; CATALYST; CHEMICAL STRUCTURE; POLYMERIZATION; SCREENING; TEMPERATURE; X RAY DIFFRACTION;

EID: 0037675228     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja020868k     Document Type: Article

References (93)

1. For selected reviews on metallocenes, see: (a) Jordan, R. F. Adv. Organomet. Chem. 1991, 32, 325-387. (b) Kashiwa, N.; Imuta, J.,-i. Catal. Surv. Jpn. 1997, 1, 125 -142. (c) McKnight, A. L.; Waymouth, R. M. Chem. Rev. 1998, 98, 2587-2598. (d) Brintzinger, H. H.; Fischer, D.; Mülhaupt, R.; Rieger, B. Waymouth, R. M. Angew. Chem., Int. Ed. Engl. 1995, 34, 1143-1170. (e) Bochmann, M. J. Chem. Soc., Dalton Trans. 1996, 255-270. (f) Alt, H. G.; Köppl, A. Chem. Rev. 2000, 100, 1205-1221.
2. For selected reviews on metallocenes, see: (a) Jordan, R. F. Adv. Organomet. Chem. 1991, 32, 325-387. (b) Kashiwa, N.; Imuta, J.,-i. Catal. Surv. Jpn. 1997, 1, 125 -142. (c) McKnight, A. L.; Waymouth, R. M. Chem. Rev. 1998, 98, 2587-2598. (d) Brintzinger, H. H.; Fischer, D.; Mülhaupt, R.; Rieger, B. Waymouth, R. M. Angew. Chem., Int. Ed. Engl. 1995, 34, 1143-1170. (e) Bochmann, M. J. Chem. Soc., Dalton Trans. 1996, 255-270. (f) Alt, H. G.; Köppl, A. Chem. Rev. 2000, 100, 1205-1221.
3. For selected reviews on metallocenes, see: (a) Jordan, R. F. Adv. Organomet. Chem. 1991, 32, 325-387. (b) Kashiwa, N.; Imuta, J.,-i. Catal. Surv. Jpn. 1997, 1, 125 -142. (c) McKnight, A. L.; Waymouth, R. M. Chem. Rev. 1998, 98, 2587-2598. (d) Brintzinger, H. H.; Fischer, D.; Mülhaupt, R.; Rieger, B. Waymouth, R. M. Angew. Chem., Int. Ed. Engl. 1995, 34, 1143-1170. (e) Bochmann, M. J. Chem. Soc., Dalton Trans. 1996, 255-270. (f) Alt, H. G.; Köppl, A. Chem. Rev. 2000, 100, 1205-1221.
4. For selected reviews on metallocenes, see: (a) Jordan, R. F. Adv. Organomet. Chem. 1991, 32, 325-387. (b) Kashiwa, N.; Imuta, J.,-i. Catal. Surv. Jpn. 1997, 1, 125 -142. (c) McKnight, A. L.; Waymouth, R. M. Chem. Rev. 1998, 98, 2587-2598. (d) Brintzinger, H. H.; Fischer, D.; Mülhaupt, R.; Rieger, B. Waymouth, R. M. Angew. Chem., Int. Ed. Engl. 1995, 34, 1143-1170. (e) Bochmann, M. J. Chem. Soc., Dalton Trans. 1996, 255-270. (f) Alt, H. G.; Köppl, A. Chem. Rev. 2000, 100, 1205-1221.
5. For selected reviews on metallocenes, see: (a) Jordan, R. F. Adv. Organomet. Chem. 1991, 32, 325-387. (b) Kashiwa, N.; Imuta, J.,-i. Catal. Surv. Jpn. 1997, 1, 125 -142. (c) McKnight, A. L.; Waymouth, R. M. Chem. Rev. 1998, 98, 2587-2598. (d) Brintzinger, H. H.; Fischer, D.; Mülhaupt, R.; Rieger, B. Waymouth, R. M. Angew. Chem., Int. Ed. Engl. 1995, 34, 1143-1170. (e) Bochmann, M. J. Chem. Soc., Dalton Trans. 1996, 255-270. (f) Alt, H. G.; Köppl, A. Chem. Rev. 2000, 100, 1205-1221.
6. For selected reviews on metallocenes, see: (a) Jordan, R. F. Adv. Organomet. Chem. 1991, 32, 325-387. (b) Kashiwa, N.; Imuta, J.,-i. Catal. Surv. Jpn. 1997, 1, 125 -142. (c) McKnight, A. L.; Waymouth, R. M. Chem. Rev. 1998, 98, 2587-2598. (d) Brintzinger, H. H.; Fischer, D.; Mülhaupt, R.; Rieger, B. Waymouth, R. M. Angew. Chem., Int. Ed. Engl. 1995, 34, 1143-1170. (e) Bochmann, M. J. Chem. Soc., Dalton Trans. 1996, 255-270. (f) Alt, H. G.; Köppl, A. Chem. Rev. 2000, 100, 1205-1221.
7. For a review of the polyolefin field, refer to articles within: Chem. Rev. 2000, Volume 100.
8. (a) Turner, H. W. U. S. Patent 4,752,597, 1988.
9. (b) Turner, H. W.; Hlatky, G. G.; Eckman, R. R. U. S. Patent 5,470,927, 1995.
10. (c) Stevens, J. C.; Timmers, F. J.; Wilson, D. R.; Schmidt, G. F.; Nickias, P. N.; Rosen, R. K.; Knight, G. W.; Lai, S-y, Eur. Patent Appl. 416-815-A2, 1991.
11. (d) Stevens, J. C.; Neithamer, D. R. Eur. Patent Appl. 418-044-A2, 1991.
12. (e) Stevens, J. C.; Neithamer, D. R. U. S. Patent 5,064,802, 1991.
13. (f) Canich, J. A. M.; Licciardi, G. F. U. S. Patent 5, 057, 475, 1991.
14. See ref 6 and: Baumann, R.; (a) Davis, W. M.; Schrock, R. R. J. Am. Chem. Soc. 1997, 119, 3830-3831.
15. (b) Liang, L.-C.; Schrock, R. R.; Davis, W. M.; McConville, D. H. J. Am. Chem. Soc. 1999, 121, 5797-5798.
16. (c) Scollard, J. D. McConville, D. H. J. Am. Chem. Soc. 1996, 118, 10 008-10 009.
17. (d) Tshuva, E. Y.; Goldberg, I.; Kol, M.; Goldschmidt, Z. J. Chem. Soc. Chem. Commun. 2001, 2120-2121.
18. (e) Tshuva, E. Y.; Goldberg, I.; Kol, M. Goldschmidt, Z. Organometallics, 2001, 20, 3017-3028.
19. (f) Matsui. S.; Mitani, M.; Saito, J.; Tohi, Y.; Makio, H.; Matsukawa, N.; Takagi, Y.; Tsuru, K.; Nitabaru, M.; Nakano, T.; Tanaka, H.; Kashiwa, N.; Fujita, T. J. Am. Chem. Soc. 2001, 123, 6847-6856.
20. (g) Stephan, D. W.; Guérin, F.; Spence, R. E. v. H.; Koch, L.; Gao, X.; Brown, S. J.; Swabey, J. W.; Wang, Q.; Xu, W.; Zoricak, P.; Harrison, D. G. Organometallics, 1999, 18, 2046-2048.
21. (a) Ittel, S. D.; Johnson, L. K.; Brookhart, M. Chem. Rev. 2000, 100, 1169-1203.
22. (b) Johnson, L. K.; Killian, C. M.; Brookhart, M. J. Am. Chem. Soc. 1995, 117, 6414-6415.
23. (c) Small, B. L.; Brookhart, M.; Bennett, A. M. A. J. Am. Chem. Soc. 1998, 120, 4049-4050.
24. (d) Britovsek, G. J. P.; Gibson, V. C.; Kimberley, B. S.; Maddox, P. J.; McTavish, S. J.; Solan, G. A.; White, A. J. P.; Williams, D. J. J. Chem. Soc. Chem. Commun. 1998, 849-850.
25. For reviews on nonmetallocene olefin polymerization catalysts, see: (a) Britovsek, G. J. P.; Gibson, V. C.; Wass, D. F. Angew. Chem., Int. Ed. Engl. 1999, 38, 428-447. (b) Gibson, V. C.; Spitzmesser, S. K. Chem. Rev. 2002, ASAP Web Release Date Dec 17.
26. For reviews on nonmetallocene olefin polymerization catalysts, see: (a) Britovsek, G. J. P.; Gibson, V. C.; Wass, D. F. Angew. Chem., Int. Ed. Engl. 1999, 38, 428-447. (b) Gibson, V. C.; Spitzmesser, S. K. Chem. Rev. 2002, ASAP Web Release Date Dec 17.
27. For recent reviews, see: (a) Jandeleit, B.; Schaefer, D. J.; Powers, T. S.; Turner, H. W.; Weinberg, W. H. Angew. Chem., Int. Ed. Engl. 1999, 38, 2494-2532.
28. (b) Wennemers, H. Combinatorial Chemistry & High Through-put Screening 2001, 4, 273-285.
29. (c) Gennari, F.; Seneci, P.; Miertus, S. Catal. Rev.-Sci. Eng. 2000, 42(3), 385-402.
30. (d) Gennari, C.; Nestler, H. P.; Piarulli, U.; Salom, B. Liebigs Ann./Recueil 1997, 637-647.
31. (e) Shimizu, K. D.; Snapper, M. L.; Hoveyda, A. H. Chem. Eur. J. 1998, 4(10), 1885- 1889.
32. (f) Crabtree, R. H. J. Chem. Soc. Chem. Commun. 1999, 1611-1616.
33. (a) Weinberg, W. H.; McFarland, E.; Goldwasser, I.; Boussie, T.; Turner, H.; van Beek, J. A. M.; Murphy, V.; Powers, T. U.S. Patents 6, 030, 917, 2000; and 6, 248, 540, 2001.
34. (b) Weinberg, W. H.; McFarland, E.; Goldwasser, I.; Boussie, T.; Turner, H. W.; van Beek, J. A. M.; Murphy, V.; Powers, T. Eur. Patent Appl. 978-499-A2, 2000.
35. High-throughput strategies for the discovery of polyolefin catalysts are limited to a few examples; see: (a) Tian, J.; Coates, G. W. Angew. Chem., Int. Ed. Engl. 2000, 39, 3626-3629. (b) Stork, M.; Herrmann, A.; Nemnich, T.; Klapper, M.; Müllen, K. Angew. Chem. Int. Ed. Engl. 2000, 39, 4367-4369. (c) Boussie, T. R.; Coutard, C.; Turner, H.; Murphy, V.; Powers, T. S. Angew. Chem., Int. Ed. Engl. 1998, 37, 3272-3275. (d) Boussie, T. R.; Murphy, V.; Hall, K. A.; Dales, C.; Petro, M.; Carlson, E.; Turner, H. W.; Powers, T. S. Tetrahedron 1999, 55, 11699-11710. (e) Hinderling, C.; Chen. P. Angew. Chem., Int. Ed. Engl. 1999, 38, 2253-2256. (f) Jones, D. J.; Gibson, V. C.; Green, S. M.; Maddox, P. J. J. Chem. Soc. Chem. Commun. 2002, 1038-1039.
36. High-throughput strategies for the discovery of polyolefin catalysts are limited to a few examples; see: (a) Tian, J.; Coates, G. W. Angew. Chem., Int. Ed. Engl. 2000, 39, 3626-3629. (b) Stork, M.; Herrmann, A.; Nemnich, T.; Klapper, M.; Müllen, K. Angew. Chem. Int. Ed. Engl. 2000, 39, 4367-4369. (c) Boussie, T. R.; Coutard, C.; Turner, H.; Murphy, V.; Powers, T. S. Angew. Chem., Int. Ed. Engl. 1998, 37, 3272-3275. (d) Boussie, T. R.; Murphy, V.; Hall, K. A.; Dales, C.; Petro, M.; Carlson, E.; Turner, H. W.; Powers, T. S. Tetrahedron 1999, 55, 11699-11710. (e) Hinderling, C.; Chen. P. Angew. Chem., Int. Ed. Engl. 1999, 38, 2253-2256. (f) Jones, D. J.; Gibson, V. C.; Green, S. M.; Maddox, P. J. J. Chem. Soc. Chem. Commun. 2002, 1038-1039.
37. High-throughput strategies for the discovery of polyolefin catalysts are limited to a few examples; see: (a) Tian, J.; Coates, G. W. Angew. Chem., Int. Ed. Engl. 2000, 39, 3626-3629. (b) Stork, M.; Herrmann, A.; Nemnich, T.; Klapper, M.; Müllen, K. Angew. Chem. Int. Ed. Engl. 2000, 39, 4367-4369. (c) Boussie, T. R.; Coutard, C.; Turner, H.; Murphy, V.; Powers, T. S. Angew. Chem., Int. Ed. Engl. 1998, 37, 3272-3275. (d) Boussie, T. R.; Murphy, V.; Hall, K. A.; Dales, C.; Petro, M.; Carlson, E.; Turner, H. W.; Powers, T. S. Tetrahedron 1999, 55, 11699-11710. (e) Hinderling, C.; Chen. P. Angew. Chem., Int. Ed. Engl. 1999, 38, 2253-2256. (f) Jones, D. J.; Gibson, V. C.; Green, S. M.; Maddox, P. J. J. Chem. Soc. Chem. Commun. 2002, 1038-1039.
38. High-throughput strategies for the discovery of polyolefin catalysts are limited to a few examples; see: (a) Tian, J.; Coates, G. W. Angew. Chem., Int. Ed. Engl. 2000, 39, 3626-3629. (b) Stork, M.; Herrmann, A.; Nemnich, T.; Klapper, M.; Müllen, K. Angew. Chem. Int. Ed. Engl. 2000, 39, 4367-4369. (c) Boussie, T. R.; Coutard, C.; Turner, H.; Murphy, V.; Powers, T. S. Angew. Chem., Int. Ed. Engl. 1998, 37, 3272-3275. (d) Boussie, T. R.; Murphy, V.; Hall, K. A.; Dales, C.; Petro, M.; Carlson, E.; Turner, H. W.; Powers, T. S. Tetrahedron 1999, 55, 11699-11710. (e) Hinderling, C.; Chen. P. Angew. Chem., Int. Ed. Engl. 1999, 38, 2253-2256. (f) Jones, D. J.; Gibson, V. C.; Green, S. M.; Maddox, P. J. J. Chem. Soc. Chem. Commun. 2002, 1038-1039.
39. High-throughput strategies for the discovery of polyolefin catalysts are limited to a few examples; see: (a) Tian, J.; Coates, G. W. Angew. Chem., Int. Ed. Engl. 2000, 39, 3626-3629. (b) Stork, M.; Herrmann, A.; Nemnich, T.; Klapper, M.; Müllen, K. Angew. Chem. Int. Ed. Engl. 2000, 39, 4367-4369. (c) Boussie, T. R.; Coutard, C.; Turner, H.; Murphy, V.; Powers, T. S. Angew. Chem., Int. Ed. Engl. 1998, 37, 3272-3275. (d) Boussie, T. R.; Murphy, V.; Hall, K. A.; Dales, C.; Petro, M.; Carlson, E.; Turner, H. W.; Powers, T. S. Tetrahedron 1999, 55, 11699-11710. (e) Hinderling, C.; Chen. P. Angew. Chem., Int. Ed. Engl. 1999, 38, 2253-2256. (f) Jones, D. J.; Gibson, V. C.; Green, S. M.; Maddox, P. J. J. Chem. Soc. Chem. Commun. 2002, 1038-1039.
40. High-throughput strategies for the discovery of polyolefin catalysts are limited to a few examples; see: (a) Tian, J.; Coates, G. W. Angew. Chem., Int. Ed. Engl. 2000, 39, 3626-3629. (b) Stork, M.; Herrmann, A.; Nemnich, T.; Klapper, M.; Müllen, K. Angew. Chem. Int. Ed. Engl. 2000, 39, 4367-4369. (c) Boussie, T. R.; Coutard, C.; Turner, H.; Murphy, V.; Powers, T. S. Angew. Chem., Int. Ed. Engl. 1998, 37, 3272-3275. (d) Boussie, T. R.; Murphy, V.; Hall, K. A.; Dales, C.; Petro, M.; Carlson, E.; Turner, H. W.; Powers, T. S. Tetrahedron 1999, 55, 11699-11710. (e) Hinderling, C.; Chen. P. Angew. Chem., Int. Ed. Engl. 1999, 38, 2253-2256. (f) Jones, D. J.; Gibson, V. C.; Green, S. M.; Maddox, P. J. J. Chem. Soc. Chem. Commun. 2002, 1038-1039.
41. For high-throughput screening techniques, see: (a) Connolly, A. R.; Sutherland, J. D. Angew. Chem., Int. Ed. 2000, 39, 4268-4271. (b) Holzwarth, A.; Schmidt, H.-W.; Maier, W. F. Angew. Chem., Int. Ed. Engl. 1998, 37, 2644-2647. (c) Taylor, S. J.; Morken, J. P. Science 1998, 280, 267-270. (d) Stambuli, J. P.; Stauffer, S. R.; Shaughnessy, K. H.; Hartwig, J. F. J. Am. Chem. Soc. 2001, 123, 2677-2678.
42. For high-throughput screening techniques, see: (a) Connolly, A. R.; Sutherland, J. D. Angew. Chem., Int. Ed. 2000, 39, 4268-4271. (b) Holzwarth, A.; Schmidt, H.-W.; Maier, W. F. Angew. Chem., Int. Ed. Engl. 1998, 37, 2644-2647. (c) Taylor, S. J.; Morken, J. P. Science 1998, 280, 267-270. (d) Stambuli, J. P.; Stauffer, S. R.; Shaughnessy, K. H.; Hartwig, J. F. J. Am. Chem. Soc. 2001, 123, 2677-2678.
43. For high-throughput screening techniques, see: (a) Connolly, A. R.; Sutherland, J. D. Angew. Chem., Int. Ed. 2000, 39, 4268-4271. (b) Holzwarth, A.; Schmidt, H.-W.; Maier, W. F. Angew. Chem., Int. Ed. Engl. 1998, 37, 2644-2647. (c) Taylor, S. J.; Morken, J. P. Science 1998, 280, 267-270. (d) Stambuli, J. P.; Stauffer, S. R.; Shaughnessy, K. H.; Hartwig, J. F. J. Am. Chem. Soc. 2001, 123, 2677-2678.
44. For high-throughput screening techniques, see: (a) Connolly, A. R.; Sutherland, J. D. Angew. Chem., Int. Ed. 2000, 39, 4268-4271. (b) Holzwarth, A.; Schmidt, H.-W.; Maier, W. F. Angew. Chem., Int. Ed. Engl. 1998, 37, 2644-2647. (c) Taylor, S. J.; Morken, J. P. Science 1998, 280, 267-270. (d) Stambuli, J. P.; Stauffer, S. R.; Shaughnessy, K. H.; Hartwig, J. F. J. Am. Chem. Soc. 2001, 123, 2677-2678.
45. For high-throughput catalyst discovery, see ref 7 and: (a) Francis, M. B.; Jacobsen, E. N. Angew. Chem., Int. Ed. Engl. 1999, 38, 937-941. (b) Sigman, M, S.; Jacobsen, E. N. J. Am. Chem. Soc. 1998, 120, 4901-4902. (c) Porte, A. M.; Reibenspies, J.; Burgess, K. J. Am. Chem. Soc. 1998, 120, 9180-9187. (d) Gilbertson, S. R.; Collibee, S. E.; Agarkov, A. J. Am. Chem. Soc. 2000, 122, 6522-6523. (e) Loch, J. A.; Crabtree, R. H. Pure Appl. Chem. 2001, 73, 119-128. (f) Dahmen, S.; Bräse, S. Synthesis 2001, 10, 1431-1449.
46. For high-throughput catalyst discovery, see ref 7 and: (a) Francis, M. B.; Jacobsen, E. N. Angew. Chem., Int. Ed. Engl. 1999, 38, 937-941. (b) Sigman, M. S.; Jacobsen, E. N. J. Am. Chem. Soc. 1998, 120, 4901-4902. (c) Porte, A. M.; Reibenspies, J.; Burgess, K. J. Am. Chem. Soc. 1998, 120, 9180-9187. (d) Gilbertson, S. R.; Collibee, S. E.; Agarkov, A. J. Am. Chem. Soc. 2000, 122, 6522-6523. (e) Loch, J. A.; Crabtree, R. H. Pure Appl. Chem. 2001, 73, 119-128. (f) Dahmen, S.; Bräse, S. Synthesis 2001, 10, 1431-1449.
47. For high-throughput catalyst discovery, see ref 7 and: (a) Francis, M. B.; Jacobsen, E. N. Angew. Chem., Int. Ed. Engl. 1999, 38, 937-941. (b) Sigman, M. S.; Jacobsen, E. N. J. Am. Chem. Soc. 1998, 120, 4901-4902. (c) Porte, A. M.; Reibenspies, J.; Burgess, K. J. Am. Chem. Soc. 1998, 120, 9180-9187. (d) Gilbertson, S. R.; Collibee, S. E.; Agarkov, A. J. Am. Chem. Soc. 2000, 122, 6522-6523. (e) Loch, J. A.; Crabtree, R. H. Pure Appl. Chem. 2001, 73, 119-128. (f) Dahmen, S.; Bräse, S. Synthesis 2001, 10, 1431-1449.
48. For high-throughput catalyst discovery, see ref 7 and: (a) Francis, M. B.; Jacobsen, E. N. Angew. Chem., Int. Ed. Engl. 1999, 38, 937-941. (b) Sigman, M. S.; Jacobsen, E. N. J. Am. Chem. Soc. 1998, 120, 4901-4902. (c) Porte, A. M.; Reibenspies, J.; Burgess, K. J. Am. Chem. Soc. 1998, 120, 9180-9187. (d) Gilbertson, S. R.; Collibee, S. E.; Agarkov, A. J. Am. Chem. Soc. 2000, 122, 6522-6523. (e) Loch, J. A.; Crabtree, R. H. Pure Appl. Chem. 2001, 73, 119-128. (f) Dahmen, S.; Bräse, S. Synthesis 2001, 10, 1431-1449.
49. For high-throughput catalyst discovery, see ref 7 and: (a) Francis, M. B.; Jacobsen, E. N. Angew. Chem., Int. Ed. Engl. 1999, 38, 937-941. (b) Sigman, M. S.; Jacobsen, E. N. J. Am. Chem. Soc. 1998, 120, 4901-4902. (c) Porte, A. M.; Reibenspies, J.; Burgess, K. J. Am. Chem. Soc. 1998, 120, 9180-9187. (d) Gilbertson, S. R.; Collibee, S. E.; Agarkov, A. J. Am. Chem. Soc. 2000, 122, 6522-6523. (e) Loch, J. A.; Crabtree, R. H. Pure Appl. Chem. 2001, 73, 119-128. (f) Dahmen, S.; Bräse, S. Synthesis 2001, 10, 1431-1449.
50. For high-throughput catalyst discovery, see ref 7 and: (a) Francis, M. B.; Jacobsen, E. N. Angew. Chem., Int. Ed. Engl. 1999, 38, 937-941. (b) Sigman, M. S.; Jacobsen, E. N. J. Am. Chem. Soc. 1998, 120, 4901-4902. (c) Porte, A. M.; Reibenspies, J.; Burgess, K. J. Am. Chem. Soc. 1998, 120, 9180-9187. (d) Gilbertson, S. R.; Collibee, S. E.; Agarkov, A. J. Am. Chem. Soc. 2000, 122, 6522-6523. (e) Loch, J. A.; Crabtree, R. H. Pure Appl. Chem. 2001, 73, 119-128. (f) Dahmen, S.; Bräse, S. Synthesis 2001, 10, 1431-1449.
51. Pooled approaches can also be used, see refs 7 and 9.
52. (a) Nielson, R. B.; Kuebler, S. C.; Bennett, J.; Safir, A.; Petro, M. U.S. Patent 6, 175, 409, 2001; Boussie, T. R.; Devenney, M. Eur. Patent Appl. 1-160-262-A1, 2001.
53. (a) Nielson, R. B.; Kuebler, S. C.; Bennett, J.; Safir, A.; Petro, M. U.S. Patent 6, 175, 409, 2001; Boussie, T. R.; Devenney, M. Eur. Patent Appl. 1-160-262-A1, 2001.
54. (b) Komon, Z. J. A.; Diamond, G. M.; Leclerc, M. K.; Murphy, V.; Okazaki, M.; Bazan, G. C.; J. Am. Chem. Soc. 2002, 124, 15 280-15 285.
55. Linear low-density polyethylene is an ethylene-α - olefin copolymer in which the α-olefin, typically 1-hexene or 1-octene, is statistically distributed throughout the polymer chain. Commercial solution-phase polymerizations are conducted at temperatures in excess of 100 °C. New high-temperature catalysts that are capable of producing high molecular weight, high α-olefin content copolymers with high productivities are highly desirable, see: Klosin, J.; Kruper, W. J., Jr.; Nickias, P. N.; Roof, G. R.; De Waele, P.; Abboud, K. A. Organometallics 2001, 20, 2663-2665.
56. Additionally, the use of a liquid α - olefin, such as 1-octene, in a primary screening format is convenient, since this allows liquid handling robots to deliver reagents and monomer rapidly to an array of reaction vessels. Furthermore, poly-1-octene is a soluble material that can be conveniently and rapidly manipulated using automated liquid handling equipment. See: Diamond, G. M.; Goh, C.; Leclerc, M. K.; Murphy, V.; Turner, H. W. WO Patent Application 01/98371 2001.
57. Lacy, S. D.; McFarland, E. W.; Safir, A. L.; Turner, S. J.; Van Erden L.; Wang, P. WO Patent Application 00/23921, 2000; Rust, W. C.; Nielson, R. B. WO Patent Application 00/67086, 2000.
58. Lacy, S. D.; McFarland, E. W.; Safir, A. L.; Turner, S. J.; Van Erden L.; Wang, P. WO Patent Application 00/23921, 2000; Rust, W. C.; Nielson, R. B. WO Patent Application 00/67086, 2000.
59. (a) Ligand [IH] see: van der Linden, A.; Schaverien, C. J.; Meijboom, N.; Ganter, C.; Orpen, A. G. J. Am. Chem. Soc. 1995, 117, 3008-3021; Katayama, H.; Nabika, M.; Imai, A.; Kawamura, N.; Hanaoka, H. Eur. Patent Appl. 0-761-694, 1996.
60. (a) Ligand [IH] see: van der Linden, A.; Schaverien, C. J.; Meijboom, N.; Ganter, C.; Orpen, A. G. J. Am. Chem. Soc. 1995, 117, 3008-3021; Katayama, H.; Nabika, M.; Imai, A.; Kawamura, N.; Hanaoka, H. Eur. Patent Appl. 0-761-694, 1996.
61. (b) Ligand [IIH] see: Scollard, J. D.; McConville, D. H.; Vittal, J. J. Organometallics 1997, 16, 4415-4420; Shaffer, T. D.; Squire, K. R. WO Patent Application 98/37109, 1998; Imuta, J.; Saito, J.; Sugimura, K.; Fujita, T. WO Patent Application 98/34961, 1998.
62. (b) Ligand [IIH] see: Scollard, J. D.; McConville, D. H.; Vittal, J. J. Organometallics 1997, 16, 4415-4420; Shaffer, T. D.; Squire, K. R. WO Patent Application 98/37109, 1998; Imuta, J.; Saito, J.; Sugimura, K.; Fujita, T. WO Patent Application 98/34961, 1998.
63. (b) Ligand [IIH] see: Scollard, J. D.; McConville, D. H.; Vittal, J. J. Organometallics 1997, 16, 4415-4420; Shaffer, T. D.; Squire, K. R. WO Patent Application 98/37109, 1998; Imuta, J.; Saito, J.; Sugimura, K.; Fujita, T. WO Patent Application 98/34961, 1998.
64. (c) Ligand [IIIA] and [IIIB], see: Fuhrmann, H.; Brenner, S.; Arndt, P.; Kempe, R. Inorg. Chem. 1996, 35, 6742-6745. For related ligands, see: Polamo, M.; Leskelä, M.; Hakala, K.; Löfgren, B. WO Patent-Application 97/45434, 1997.
65. (c) Ligand [IIIA] and [IIIB], see: Fuhrmann, H.; Brenner, S.; Arndt, P.; Kempe, R. Inorg. Chem. 1996, 35, 6742-6745. For related ligands, see: Polamo, M.; Leskelä, M.; Hakala, K.; Löfgren, B. WO Patent-Application 97/45434, 1997.
66. (d) Ligand [IIIC] see: Nitabaru, M.; Yoshida, Y.; Mitani, M.; Terunori, F. Eur. Patent Appl. 1-008-595-A3, 2000.
67. (e) Ligand [IIID] see: Takahashi, F.; Naito, Y. JP 11060624, 1999.
68. (f) Ligand [IIIE], see: Theopold, K. H.; Kim, W.-K.; Power, J. M.; Mora, J. M.; Masino, A. P. WO Patent Application 01/12637, 2001.
69. (g) For ligands related to [IG] see: Fujita, T.; Tohi, Y.; Mitani, M.; Matsui, S.; Saito, J.; Nitabaru, M.; Sugi, K.; Makio, H.; Tsutsui, T. Eur. Patent Appl. 0-874-005-A1 1998.
70. 4) were observed. The notation [ligand] used here refers to the deprotonated ligand.
71. Siedle, A. R.; Newmark, R. A.; Schroepfer, J. N.; Lyon, P. A. Organo-metallics 1991, 10, O, 400-404.
72. 4 (M = Zr, Hf).
73. Polymer yields were determined using an automated weighing assay.
74. The catalytically active metal-ligand combinations produced poly-1-octenes with a wide range of molecular weights. Data for all 384 experiments can be found in the Supporting Information.
75. A repeat experiment in which the ligand-to-metal ratio was adjusted to 2:1 significantly altered the 1-octene conversions. However, no new catalytically active metal-ligand combinations were identified.
76. 3Al produced small quantities of a material that was not detected by our Rapid◇GPC technique. The Rapid◇GPC protocol chosen has a low molecular weight detection limit of around 1000.
77. Turner, H. W.; Dales, G. C.; Van Erden, L.; van Beek, J. A. M. U.S. Patent 6,306,658, 2000.
78. An earlier version of our parallel polymerization reactor was used for these experiments.
79. See the Supporting Information, and: (a) Wolfe, J. P.; Wagaw, S.; Marcoux, J.-F.; Buchwald, S. L. Acc. Chem. Res. 1998. 31, 805-818. (b) Hartwig, J. F. Angew. Chem., Int. Ed. Engl. 1998, 37, 2046-2067.
80. See the Supporting Information, and: (a) Wolfe, J. P.; Wagaw, S.; Marcoux, J.-F.; Buchwald, S. L. Acc. Chem. Res. 1998. 31, 805-818. (b) Hartwig, J. F. Angew. Chem., Int. Ed. Engl. 1998, 37, 2046-2067.
81. It should be noted that for bulkier ligands, particularly those containing phenyl ether moieties, we typically observe identical products, but lower polymer yields using the in situ preparation method. Thus, catalyst performance is convolved with complexation efficiency, and this limitation needs to be considered when analyzing the results of this study.
82. 4 combination.
83. 3Al: 1.97 mM.
84. Of the 24 copolymers containing > 10 wt % 1-octene, 20 had polydispersities below 3.5, see the Supporting Information.
85. Goh, C.; Diamond, G. M.; Murphy, V.; Leclerc, M. K.; Hall, K.; Lapointe, A. M.; Boussie, T. R.; Lund, C.; Uno, T. WO Patent Application 01/74910, 2001.
86. At a stirring rate of 600 rpm. The real-time ethylene uptake monitoring capabilities of these reactors enable us to readily identify catalysts that are running under ethylene diffusion limitations.
87. Under identical conditions, the results from this secondary screening experiment are reproducible.
88. The analogous zirconium compound has been reported, see: Murray, R. E. U.S. Patent 6,103,657, 2000.
89. (a) Bei, X.; Crevier, T.; Guram, A. S.; Jandeleit, B.; Powers, T. S.; Turner, H. W.; Uno, T.; Weinberg, W. H. Tetrahedron Lett. 1999, 40 (20), 3855-3858.
90. (b) Bei, X.; Guram, A. S.; Turner, H. W.; Weinberg, W. H. Tetrahedron Lett. 1999, 40 (7), 1237-1240.
91. (c) Bei, X.; Turner, H. W.; Weinberg, W. H.; Guram, A. S.; Petersen, J. L. J. Org. Chem. 1999, 64, 6797-6803.
92. (d) Bei, X.; Uno, T.; Norris, J.; Turner, H. W.; Weinberg, W. H.; Guram, A. S. Organometallics 1999, 18, 1840-1853.
93. Sheldrick, G. M. SHELXTL, An Integrated System for Solving, Refining and Displaying Crystal Structures from Diffraction Data; University of Göttingen, Göttingen, Germany, 1981.