Palladiumd(II)-catalyzed olefin addition polymerizations of 3,3-dialkyl-substituted cyclopropenes

Macromolecules

Volumn 30, Issue 24, 1997, Pages 7375-7385

  Rush, Stephen ^a   Reinmuth, Annette ^a   Risse, Wilhelm ^a  

^a UNIVERSITY COLLEGE DUBLIN   (Ireland)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSIS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; OLEFINS; PALLADIUM COMPOUNDS; RING OPENING POLYMERIZATION;

CYCLOPROPENE;

POLYMERIZATION;

EID: 0031361688     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma970701p     Document Type: Article

References (101)

1. (a) Johnson, L. K.; Mecking, S.; Brookhart, M. J. Am. Chem. Soc. 1996, 118, 267.
2. Johnson, L. K.; Killian, C. M.; Brookhart, M. J. Am. Chem. Soc. 1995, 117, 6414
3. n: (a) Sen, A. Acc. Chem. Res. 1993, 26, 303. (b) Sen, A. Adv. Polym. Sci. 1986, 73/74, 125. (c) Sen, A.; Lai, T.-W. Organometallics 1984, 3, 866. (d) Sen, A.; Lai, T.-W. J. Am. Chem. Soc. 1982, 104, 3520. (e) Drent, E.; van Broekhoven, J. A. M.; Doyle, M. J. J. Organomet. Chem. 1991, 417, 135. (f) Klabunde, U.; Ittel, S. D. J. Mol. Catal. 1987, 41, 123. (g) Drent, E. (Shell), Eur. Pat. Appl. 181014, 1985; Chem. Abstr. 1985, 105, 98172. (h) Zhao, A. X.; Chien, J. C. W. J. Polym. Sci. A, Polym. Chem. 1992, 30, 2735.
4. n: (a) Sen, A. Acc. Chem. Res. 1993, 26, 303. (b) Sen, A. Adv. Polym. Sci. 1986, 73/74, 125. (c) Sen, A.; Lai, T.-W. Organometallics 1984, 3, 866. (d) Sen, A.; Lai, T.-W. J. Am. Chem. Soc. 1982, 104, 3520. (e) Drent, E.; van Broekhoven, J. A. M.; Doyle, M. J. J. Organomet. Chem. 1991, 417, 135. (f) Klabunde, U.; Ittel, S. D. J. Mol. Catal. 1987, 41, 123. (g) Drent, E. (Shell), Eur. Pat. Appl. 181014, 1985; Chem. Abstr. 1985, 105, 98172. (h) Zhao, A. X.; Chien, J. C. W. J. Polym. Sci. A, Polym. Chem. 1992, 30, 2735.
5. n: (a) Sen, A. Acc. Chem. Res. 1993, 26, 303. (b) Sen, A. Adv. Polym. Sci. 1986, 73/74, 125. (c) Sen, A.; Lai, T.-W. Organometallics 1984, 3, 866. (d) Sen, A.; Lai, T.-W. J. Am. Chem. Soc. 1982, 104, 3520. (e) Drent, E.; van Broekhoven, J. A. M.; Doyle, M. J. J. Organomet. Chem. 1991, 417, 135. (f) Klabunde, U.; Ittel, S. D. J. Mol. Catal. 1987, 41, 123. (g) Drent, E. (Shell), Eur. Pat. Appl. 181014, 1985; Chem. Abstr. 1985, 105, 98172. (h) Zhao, A. X.; Chien, J. C. W. J. Polym. Sci. A, Polym. Chem. 1992, 30, 2735.
6. n: (a) Sen, A. Acc. Chem. Res. 1993, 26, 303. (b) Sen, A. Adv. Polym. Sci. 1986, 73/74, 125. (c) Sen, A.; Lai, T.-W. Organometallics 1984, 3, 866. (d) Sen, A.; Lai, T.-W. J. Am. Chem. Soc. 1982, 104, 3520. (e) Drent, E.; van Broekhoven, J. A. M.; Doyle, M. J. J. Organomet. Chem. 1991, 417, 135. (f) Klabunde, U.; Ittel, S. D. J. Mol. Catal. 1987, 41, 123. (g) Drent, E. (Shell), Eur. Pat. Appl. 181014, 1985; Chem. Abstr. 1985, 105, 98172. (h) Zhao, A. X.; Chien, J. C. W. J. Polym. Sci. A, Polym. Chem. 1992, 30, 2735.
7. n: (a) Sen, A. Acc. Chem. Res. 1993, 26, 303. (b) Sen, A. Adv. Polym. Sci. 1986, 73/74, 125. (c) Sen, A.; Lai, T.-W. Organometallics 1984, 3, 866. (d) Sen, A.; Lai, T.-W. J. Am. Chem. Soc. 1982, 104, 3520. (e) Drent, E.; van Broekhoven, J. A. M.; Doyle, M. J. J. Organomet. Chem. 1991, 417, 135. (f) Klabunde, U.; Ittel, S. D. J. Mol. Catal. 1987, 41, 123. (g) Drent, E. (Shell), Eur. Pat. Appl. 181014, 1985; Chem. Abstr. 1985, 105, 98172. (h) Zhao, A. X.; Chien, J. C. W. J. Polym. Sci. A, Polym. Chem. 1992, 30, 2735.
8. n: (a) Sen, A. Acc. Chem. Res. 1993, 26, 303. (b) Sen, A. Adv. Polym. Sci. 1986, 73/74, 125. (c) Sen, A.; Lai, T.-W. Organometallics 1984, 3, 866. (d) Sen, A.; Lai, T.-W. J. Am. Chem. Soc. 1982, 104, 3520. (e) Drent, E.; van Broekhoven, J. A. M.; Doyle, M. J. J. Organomet. Chem. 1991, 417, 135. (f) Klabunde, U.; Ittel, S. D. J. Mol. Catal. 1987, 41, 123. (g) Drent, E. (Shell), Eur. Pat. Appl. 181014, 1985; Chem. Abstr. 1985, 105, 98172. (h) Zhao, A. X.; Chien, J. C. W. J. Polym. Sci. A, Polym. Chem. 1992, 30, 2735.
9. n: (a) Sen, A. Acc. Chem. Res. 1993, 26, 303. (b) Sen, A. Adv. Polym. Sci. 1986, 73/74, 125. (c) Sen, A.; Lai, T.-W. Organometallics 1984, 3, 866. (d) Sen, A.; Lai, T.-W. J. Am. Chem. Soc. 1982, 104, 3520. (e) Drent, E.; van Broekhoven, J. A. M.; Doyle, M. J. J. Organomet. Chem. 1991, 417, 135. (f) Klabunde, U.; Ittel, S. D. J. Mol. Catal. 1987, 41, 123. (g) Drent, E. (Shell), Eur. Pat. Appl. 181014, 1985; Chem. Abstr. 1985, 105, 98172. (h) Zhao, A. X.; Chien, J. C. W. J. Polym. Sci. A, Polym. Chem. 1992, 30, 2735.
10. n: (a) Sen, A. Acc. Chem. Res. 1993, 26, 303. (b) Sen, A. Adv. Polym. Sci. 1986, 73/74, 125. (c) Sen, A.; Lai, T.-W. Organometallics 1984, 3, 866. (d) Sen, A.; Lai, T.-W. J. Am. Chem. Soc. 1982, 104, 3520. (e) Drent, E.; van Broekhoven, J. A. M.; Doyle, M. J. J. Organomet. Chem. 1991, 417, 135. (f) Klabunde, U.; Ittel, S. D. J. Mol. Catal. 1987, 41, 123. (g) Drent, E. (Shell), Eur. Pat. Appl. 181014, 1985; Chem. Abstr. 1985, 105, 98172. (h) Zhao, A. X.; Chien, J. C. W. J. Polym. Sci. A, Polym. Chem. 1992, 30, 2735.
11. n: (a) Brookhart, M.; Wagner, M. I. J. Am. Chem. Soc. 1996, 118, 7219. (b) Brookhart, M.; Wagner, M. L; Balavoine, G. G. A.; Ait Haddou, H. J. Am. Chem. Soc. 1994, 116, 3641. (c) Brookhart, M.; Rix, C. R.; DeSimone, J. M. J. Am. Chem. Soc. 1992, 114, 5894. (d) Corradini, P.; DeRossa, C.; Panuzzi, A.; Petrucci, G; Pino, P. Chimia 1990, 44, 52. (e) Barsacchi, M.; Consiglio, G.; Medici, L., Petrucci, G.; Suter, U. W. Angew. Chem., Int. Ed. Engl. 1991, 30, 989. (f) Drent, E. Eur. Pat. Appl. EP 229,-408, 1986.
12. n: (a) Brookhart, M.; Wagner, M. I. J. Am. Chem. Soc. 1996, 118, 7219. (b) Brookhart, M.; Wagner, M. L; Balavoine, G. G. A.; Ait Haddou, H. J. Am. Chem. Soc. 1994, 116, 3641. (c) Brookhart, M.; Rix, C. R.; DeSimone, J. M. J. Am. Chem. Soc. 1992, 114, 5894. (d) Corradini, P.; DeRossa, C.; Panuzzi, A.; Petrucci, G; Pino, P. Chimia 1990, 44, 52. (e) Barsacchi, M.; Consiglio, G.; Medici, L., Petrucci, G.; Suter, U. W. Angew. Chem., Int. Ed. Engl. 1991, 30, 989. (f) Drent, E. Eur. Pat. Appl. EP 229,-408, 1986.
13. n: (a) Brookhart, M.; Wagner, M. I. J. Am. Chem. Soc. 1996, 118, 7219. (b) Brookhart, M.; Wagner, M. L; Balavoine, G. G. A.; Ait Haddou, H. J. Am. Chem. Soc. 1994, 116, 3641. (c) Brookhart, M.; Rix, C. R.; DeSimone, J. M. J. Am. Chem. Soc. 1992, 114, 5894. (d) Corradini, P.; DeRossa, C.; Panuzzi, A.; Petrucci, G; Pino, P. Chimia 1990, 44, 52. (e) Barsacchi, M.; Consiglio, G.; Medici, L., Petrucci, G.; Suter, U. W. Angew. Chem., Int. Ed. Engl. 1991, 30, 989. (f) Drent, E. Eur. Pat. Appl. EP 229,-408, 1986.
14. n: (a) Brookhart, M.; Wagner, M. I. J. Am. Chem. Soc. 1996, 118, 7219. (b) Brookhart, M.; Wagner, M. L; Balavoine, G. G. A.; Ait Haddou, H. J. Am. Chem. Soc. 1994, 116, 3641. (c) Brookhart, M.; Rix, C. R.; DeSimone, J. M. J. Am. Chem. Soc. 1992, 114, 5894. (d) Corradini, P.; DeRossa, C.; Panuzzi, A.; Petrucci, G; Pino, P. Chimia 1990, 44, 52. (e) Barsacchi, M.; Consiglio, G.; Medici, L., Petrucci, G.; Suter, U. W. Angew. Chem., Int. Ed. Engl. 1991, 30, 989. (f) Drent, E. Eur. Pat. Appl. EP 229,-408, 1986.
15. n: (a) Brookhart, M.; Wagner, M. I. J. Am. Chem. Soc. 1996, 118, 7219. (b) Brookhart, M.; Wagner, M. L; Balavoine, G. G. A.; Ait Haddou, H. J. Am. Chem. Soc. 1994, 116, 3641. (c) Brookhart, M.; Rix, C. R.; DeSimone, J. M. J. Am. Chem. Soc. 1992, 114, 5894. (d) Corradini, P.; DeRossa, C.; Panuzzi, A.; Petrucci, G; Pino, P. Chimia 1990, 44, 52. (e) Barsacchi, M.; Consiglio, G.; Medici, L., Petrucci, G.; Suter, U. W. Angew. Chem., Int. Ed. Engl. 1991, 30, 989. (f) Drent, E. Eur. Pat. Appl. EP 229,-408, 1986.
16. n: (a) Brookhart, M.; Wagner, M. I. J. Am. Chem. Soc. 1996, 118, 7219. (b) Brookhart, M.; Wagner, M. L; Balavoine, G. G. A.; Ait Haddou, H. J. Am. Chem. Soc. 1994, 116, 3641. (c) Brookhart, M.; Rix, C. R.; DeSimone, J. M. J. Am. Chem. Soc. 1992, 114, 5894. (d) Corradini, P.; DeRossa, C.; Panuzzi, A.; Petrucci, G; Pino, P. Chimia 1990, 44, 52. (e) Barsacchi, M.; Consiglio, G.; Medici, L., Petrucci, G.; Suter, U. W. Angew. Chem., Int. Ed. Engl. 1991, 30, 989. (f) Drent, E. Eur. Pat. Appl. EP 229,-408, 1986.
17. n oligomers and polymers (including polymers with spiroketal units): (a) Jiang, Z.; Sen, A. J. Am. Chem. Soc. 1995, 117, 4455. (b) Sperrle, M.; Consiglio, G. J. Am. Chem. Soc. 1995, 117, 12130. (c) Bronco, S.; Consiglio, G.; Hutter, R. Batistini, A.; Suter, U. W. Macromolecules 1994, 27, 4436. (d) Barsacchi, M.; Batistini, A.; Consiglio, G.; Suter, U. W. Macromolecules 1992, 25, 3604. (e) Batistini, A.; Consiglio, G. Suter, U. W. Angew. Chem., Int. Ed. Engl. 1992, 31, 303. (f) Drent, E.; Wife, R. L. U.S. Patent 4,970,294, 1990. (g) Xu, F. Y.; Zhao, A. X.; Chien, J. C. W. Makromol. Chem. 1993, 194, 2579. (h) Abu-Surrah, A. S.; Wursche, R.; Rieger, B.; Eckert, G.; Pechhold, W. Macromolecules 1996, 29, 4806.
18. n oligomers and polymers (including polymers with spiroketal units): (a) Jiang, Z.; Sen, A. J. Am. Chem. Soc. 1995, 117, 4455. (b) Sperrle, M.; Consiglio, G. J. Am. Chem. Soc. 1995, 117, 12130. (c) Bronco, S.; Consiglio, G.; Hutter, R. Batistini, A.; Suter, U. W. Macromolecules 1994, 27, 4436. (d) Barsacchi, M.; Batistini, A.; Consiglio, G.; Suter, U. W. Macromolecules 1992, 25, 3604. (e) Batistini, A.; Consiglio, G. Suter, U. W. Angew. Chem., Int. Ed. Engl. 1992, 31, 303. (f) Drent, E.; Wife, R. L. U.S. Patent 4,970,294, 1990. (g) Xu, F. Y.; Zhao, A. X.; Chien, J. C. W. Makromol. Chem. 1993, 194, 2579. (h) Abu-Surrah, A. S.; Wursche, R.; Rieger, B.; Eckert, G.; Pechhold, W. Macromolecules 1996, 29, 4806.
19. n oligomers and polymers (including polymers with spiroketal units): (a) Jiang, Z.; Sen, A. J. Am. Chem. Soc. 1995, 117, 4455. (b) Sperrle, M.; Consiglio, G. J. Am. Chem. Soc. 1995, 117, 12130. (c) Bronco, S.; Consiglio, G.; Hutter, R. Batistini, A.; Suter, U. W. Macromolecules 1994, 27, 4436. (d) Barsacchi, M.; Batistini, A.; Consiglio, G.; Suter, U. W. Macromolecules 1992, 25, 3604. (e) Batistini, A.; Consiglio, G. Suter, U. W. Angew. Chem., Int. Ed. Engl. 1992, 31, 303. (f) Drent, E.; Wife, R. L. U.S. Patent 4,970,294, 1990. (g) Xu, F. Y.; Zhao, A. X.; Chien, J. C. W. Makromol. Chem. 1993, 194, 2579. (h) Abu-Surrah, A. S.; Wursche, R.; Rieger, B.; Eckert, G.; Pechhold, W. Macromolecules 1996, 29, 4806.
20. n oligomers and polymers (including polymers with spiroketal units): (a) Jiang, Z.; Sen, A. J. Am. Chem. Soc. 1995, 117, 4455. (b) Sperrle, M.; Consiglio, G. J. Am. Chem. Soc. 1995, 117, 12130. (c) Bronco, S.; Consiglio, G.; Hutter, R. Batistini, A.; Suter, U. W. Macromolecules 1994, 27, 4436. (d) Barsacchi, M.; Batistini, A.; Consiglio, G.; Suter, U. W. Macromolecules 1992, 25, 3604. (e) Batistini, A.; Consiglio, G. Suter, U. W. Angew. Chem., Int. Ed. Engl. 1992, 31, 303. (f) Drent, E.; Wife, R. L. U.S. Patent 4,970,294, 1990. (g) Xu, F. Y.; Zhao, A. X.; Chien, J. C. W. Makromol. Chem. 1993, 194, 2579. (h) Abu-Surrah, A. S.; Wursche, R.; Rieger, B.; Eckert, G.; Pechhold, W. Macromolecules 1996, 29, 4806.
21. n oligomers and polymers (including polymers with spiroketal units): (a) Jiang, Z.; Sen, A. J. Am. Chem. Soc. 1995, 117, 4455. (b) Sperrle, M.; Consiglio, G. J. Am. Chem. Soc. 1995, 117, 12130. (c) Bronco, S.; Consiglio, G.; Hutter, R. Batistini, A.; Suter, U. W. Macromolecules 1994, 27, 4436. (d) Barsacchi, M.; Batistini, A.; Consiglio, G.; Suter, U. W. Macromolecules 1992, 25, 3604. (e) Batistini, A.; Consiglio, G. Suter, U. W. Angew. Chem., Int. Ed. Engl. 1992, 31, 303. (f) Drent, E.; Wife, R. L. U.S. Patent 4,970,294, 1990. (g) Xu, F. Y.; Zhao, A. X.; Chien, J. C. W. Makromol. Chem. 1993, 194, 2579. (h) Abu-Surrah, A. S.; Wursche, R.; Rieger, B.; Eckert, G.; Pechhold, W. Macromolecules 1996, 29, 4806.
22. n oligomers and polymers (including polymers with spiroketal units): (a) Jiang, Z.; Sen, A. J. Am. Chem. Soc. 1995, 117, 4455. (b) Sperrle, M.; Consiglio, G. J. Am. Chem. Soc. 1995, 117, 12130. (c) Bronco, S.; Consiglio, G.; Hutter, R. Batistini, A.; Suter, U. W. Macromolecules 1994, 27, 4436. (d) Barsacchi, M.; Batistini, A.; Consiglio, G.; Suter, U. W. Macromolecules 1992, 25, 3604. (e) Batistini, A.; Consiglio, G. Suter, U. W. Angew. Chem., Int. Ed. Engl. 1992, 31, 303. (f) Drent, E.; Wife, R. L. U.S. Patent 4,970,294, 1990. (g) Xu, F. Y.; Zhao, A. X.; Chien, J. C. W. Makromol. Chem. 1993, 194, 2579. (h) Abu-Surrah, A. S.; Wursche, R.; Rieger, B.; Eckert, G.; Pechhold, W. Macromolecules 1996, 29, 4806.
23. n oligomers and polymers (including polymers with spiroketal units): (a) Jiang, Z.; Sen, A. J. Am. Chem. Soc. 1995, 117, 4455. (b) Sperrle, M.; Consiglio, G. J. Am. Chem. Soc. 1995, 117, 12130. (c) Bronco, S.; Consiglio, G.; Hutter, R. Batistini, A.; Suter, U. W. Macromolecules 1994, 27, 4436. (d) Barsacchi, M.; Batistini, A.; Consiglio, G.; Suter, U. W. Macromolecules 1992, 25, 3604. (e) Batistini, A.; Consiglio, G. Suter, U. W. Angew. Chem., Int. Ed. Engl. 1992, 31, 303. (f) Drent, E.; Wife, R. L. U.S. Patent 4,970,294, 1990. (g) Xu, F. Y.; Zhao, A. X.; Chien, J. C. W. Makromol. Chem. 1993, 194, 2579. (h) Abu-Surrah, A. S.; Wursche, R.; Rieger, B.; Eckert, G.; Pechhold, W. Macromolecules 1996, 29, 4806.
24. n oligomers and polymers (including polymers with spiroketal units): (a) Jiang, Z.; Sen, A. J. Am. Chem. Soc. 1995, 117, 4455. (b) Sperrle, M.; Consiglio, G. J. Am. Chem. Soc. 1995, 117, 12130. (c) Bronco, S.; Consiglio, G.; Hutter, R. Batistini, A.; Suter, U. W. Macromolecules 1994, 27, 4436. (d) Barsacchi, M.; Batistini, A.; Consiglio, G.; Suter, U. W. Macromolecules 1992, 25, 3604. (e) Batistini, A.; Consiglio, G. Suter, U. W. Angew. Chem., Int. Ed. Engl. 1992, 31, 303. (f) Drent, E.; Wife, R. L. U.S. Patent 4,970,294, 1990. (g) Xu, F. Y.; Zhao, A. X.; Chien, J. C. W. Makromol. Chem. 1993, 194, 2579. (h) Abu-Surrah, A. S.; Wursche, R.; Rieger, B.; Eckert, G.; Pechhold, W. Macromolecules 1996, 29, 4806.
25. References about alternating copolymers of cyclopentene and CO: (a) Ameor, E.; Bronco, S.; Consiglio, G.; Di Benedetto, S. Macomol. Symp. 1995, 89, 443. (b) Liaw, D.-J. J. Polym. Sci., Part A: Polym. Chem. 1993, 31, 309.
26. References about alternating copolymers of cyclopentene and CO: (a) Ameor, E.; Bronco, S.; Consiglio, G.; Di Benedetto, S. Macomol. Symp. 1995, 89, 443. (b) Liaw, D.-J. J. Polym. Sci., Part A: Polym. Chem. 1993, 31, 309.
27. (a) Mathew, J. P.; Reinmuth, A.; Melia, J.; Swords, N.; Risse, W. Macromolecules 1996, 29, 2755.
28. (b) Melia, J.; Rush, S.; Mathew, J. P., Connor, E.; Mehler, C.; Risse, W. Macromol. Symp. 1995, 89, 433.
29. (c) Safir, A. L.; Novak, B. M. Macromolecules 1995, 28, 5396.
30. (d) Safir, A. L.; Novak, B. M. Macromolecules 1993, 26, 4072.
31. (e) Mehler, C.; Risse, W. Makromol. Chem., Rapid Commun. 1992, 13, 455.
32. (f) Mehler, C.; Risse, W. Macromolecules 1992, 25, 4226.
33. (g) Breunig, S.; Risse, W. Makromol. Chem. 1992, 193, 2915.
34. (h) Sen, A.; Lai, T.-W.; Thomas, R. R. J. Organomet. Chem. 1988, 358, 567.
35. (i) Sen, A.; Lai, T.-W. Organometallics 1982, 1, 415.
36. (k) Tanielian, C.; Kiennemann, A.; Osparpucu, T. Can. J. Chem. 1979, 57, 2022.
37. (l) Gaylord, N. G.; Deshpande, A. B.; Mandai, B. M., Martan, M. J. Macromol. Sci., Chem. 1977, A11, 1053.
38. (m) Corner, T.; Foster, R. G.; Hepworth, P. Polymer 1969, 10, 393.
39. (n) De Kock, R. J.; Veermans, Makromol. Chem. 1969, 95, 179.
40. (o) Schulz, R. G. Polym. Lett. 1966, 4, 541.
41. 8f,g (a) Sartori, G.; Ciampelli, F. C.; Camelli, N. Chim. Ind. (Milan) 1963, 45, 1478. (b) Tsujino, T.; Saegusa, T.; Furukawa, J. Makromol. Chem. 1965, 85, 71. (c) Kaminsky, W.; Arndt, M. Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 1994, 35 (2), 520. (d) Kaminsky, W.; Bark, A.; Arndt, M.; Makromol. Chem., Macromol. Symp. 1991, 47, 83. (e) Goodall, B. L.; McIntosh, L. H.; Rhodes, L. F. Macromol. Symp. 1995, 89, 421. (f) Maezawa, H.; Matsumoto, J.; Aiura, H.; Asahi, S. (Idemitsu Kosan Co. Ltd., Jpn.). Eur. Pat. Appl. 445 755 A2, 1991. (g) Goodall, B. L.; Benedikt, G. M.; McIntosh, L. H.; Barnes, D. A. (BF Goodrich). U. S. Patent 5 468 819, 1995.
42. 8f,g (a) Sartori, G.; Ciampelli, F. C.; Camelli, N. Chim. Ind. (Milan) 1963, 45, 1478. (b) Tsujino, T.; Saegusa, T.; Furukawa, J. Makromol. Chem. 1965, 85, 71. (c) Kaminsky, W.; Arndt, M. Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 1994, 35 (2), 520. (d) Kaminsky, W.; Bark, A.; Arndt, M.; Makromol. Chem., Macromol. Symp. 1991, 47, 83. (e) Goodall, B. L.; McIntosh, L. H.; Rhodes, L. F. Macromol. Symp. 1995, 89, 421. (f) Maezawa, H.; Matsumoto, J.; Aiura, H.; Asahi, S. (Idemitsu Kosan Co. Ltd., Jpn.). Eur. Pat. Appl. 445 755 A2, 1991. (g) Goodall, B. L.; Benedikt, G. M.; McIntosh, L. H.; Barnes, D. A. (BF Goodrich). U. S. Patent 5 468 819, 1995.
43. 8f,g (a) Sartori, G.; Ciampelli, F. C.; Camelli, N. Chim. Ind. (Milan) 1963, 45, 1478. (b) Tsujino, T.; Saegusa, T.; Furukawa, J. Makromol. Chem. 1965, 85, 71. (c) Kaminsky, W.; Arndt, M. Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 1994, 35 (2), 520. (d) Kaminsky, W.; Bark, A.; Arndt, M.; Makromol. Chem., Macromol. Symp. 1991, 47, 83. (e) Goodall, B. L.; McIntosh, L. H.; Rhodes, L. F. Macromol. Symp. 1995, 89, 421. (f) Maezawa, H.; Matsumoto, J.; Aiura, H.; Asahi, S. (Idemitsu Kosan Co. Ltd., Jpn.). Eur. Pat. Appl. 445 755 A2, 1991. (g) Goodall, B. L.; Benedikt, G. M.; McIntosh, L. H.; Barnes, D. A. (BF Goodrich). U. S. Patent 5 468 819, 1995.
44. 8f,g (a) Sartori, G.; Ciampelli, F. C.; Camelli, N. Chim. Ind. (Milan) 1963, 45, 1478. (b) Tsujino, T.; Saegusa, T.; Furukawa, J. Makromol. Chem. 1965, 85, 71. (c) Kaminsky, W.; Arndt, M. Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 1994, 35 (2), 520. (d) Kaminsky, W.; Bark, A.; Arndt, M.; Makromol. Chem., Macromol. Symp. 1991, 47, 83. (e) Goodall, B. L.; McIntosh, L. H.; Rhodes, L. F. Macromol. Symp. 1995, 89, 421. (f) Maezawa, H.; Matsumoto, J.; Aiura, H.; Asahi, S. (Idemitsu Kosan Co. Ltd., Jpn.). Eur. Pat. Appl. 445 755 A2, 1991. (g) Goodall, B. L.; Benedikt, G. M.; McIntosh, L. H.; Barnes, D. A. (BF Goodrich). U. S. Patent 5 468 819, 1995.
45. 8f,g (a) Sartori, G.; Ciampelli, F. C.; Camelli, N. Chim. Ind. (Milan) 1963, 45, 1478. (b) Tsujino, T.; Saegusa, T.; Furukawa, J. Makromol. Chem. 1965, 85, 71. (c) Kaminsky, W.; Arndt, M. Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 1994, 35 (2), 520. (d) Kaminsky, W.; Bark, A.; Arndt, M.; Makromol. Chem., Macromol. Symp. 1991, 47, 83. (e) Goodall, B. L.; McIntosh, L. H.; Rhodes, L. F. Macromol. Symp. 1995, 89, 421. (f) Maezawa, H.; Matsumoto, J.; Aiura, H.; Asahi, S. (Idemitsu Kosan Co. Ltd., Jpn.). Eur. Pat. Appl. 445 755 A2, 1991. (g) Goodall, B. L.; Benedikt, G. M.; McIntosh, L. H.; Barnes, D. A. (BF Goodrich). U. S. Patent 5 468 819, 1995.
46. 8f,g (a) Sartori, G.; Ciampelli, F. C.; Camelli, N. Chim. Ind. (Milan) 1963, 45, 1478. (b) Tsujino, T.; Saegusa, T.; Furukawa, J. Makromol. Chem. 1965, 85, 71. (c) Kaminsky, W.; Arndt, M. Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 1994, 35 (2), 520. (d) Kaminsky, W.; Bark, A.; Arndt, M.; Makromol. Chem., Macromol. Symp. 1991, 47, 83. (e) Goodall, B. L.; McIntosh, L. H.; Rhodes, L. F. Macromol. Symp. 1995, 89, 421. (f) Maezawa, H.; Matsumoto, J.; Aiura, H.; Asahi, S. (Idemitsu Kosan Co. Ltd., Jpn.). Eur. Pat. Appl. 445 755 A2, 1991. (g) Goodall, B. L.; Benedikt, G. M.; McIntosh, L. H.; Barnes, D. A. (BF Goodrich). U. S. Patent 5 468 819, 1995.
47. 8f,g (a) Sartori, G.; Ciampelli, F. C.; Camelli, N. Chim. Ind. (Milan) 1963, 45, 1478. (b) Tsujino, T.; Saegusa, T.; Furukawa, J. Makromol. Chem. 1965, 85, 71. (c) Kaminsky, W.; Arndt, M. Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 1994, 35 (2), 520. (d) Kaminsky, W.; Bark, A.; Arndt, M.; Makromol. Chem., Macromol. Symp. 1991, 47, 83. (e) Goodall, B. L.; McIntosh, L. H.; Rhodes, L. F. Macromol. Symp. 1995, 89, 421. (f) Maezawa, H.; Matsumoto, J.; Aiura, H.; Asahi, S. (Idemitsu Kosan Co. Ltd., Jpn.). Eur. Pat. Appl. 445 755 A2, 1991. (g) Goodall, B. L.; Benedikt, G. M.; McIntosh, L. H.; Barnes, D. A. (BF Goodrich). U. S. Patent 5 468 819, 1995.
48. By contrast, most transition metal catalysts induce ring-opening olefin metathesis polymerization (ROMP) of nor-bornene based monomers leading to polymer structures containing ring-opened repeating units: (a) Novak, B.; Risse, W.; Grubbs, R. H. Advances in Polymer Science; Springer Verlag: New York, 1992; Vol. 102; p 47. (b) Schrock, R. R. Acc. Chem. Res. 1990, 23, 158. (c) Ivin, K. J. Olefin Metathesis, Academic Press: London, 1983.
49. By contrast, most transition metal catalysts induce ring-opening olefin metathesis polymerization (ROMP) of nor-bornene based monomers leading to polymer structures containing ring-opened repeating units: (a) Novak, B.; Risse, W.; Grubbs, R. H. Advances in Polymer Science; Springer Verlag: New York, 1992; Vol. 102; p 47. (b) Schrock, R. R. Acc. Chem. Res. 1990, 23, 158. (c) Ivin, K. J. Olefin Metathesis, Academic Press: London, 1983.
50. By contrast, most transition metal catalysts induce ring-opening olefin metathesis polymerization (ROMP) of nor-bornene based monomers leading to polymer structures containing ring-opened repeating units: (a) Novak, B.; Risse, W.; Grubbs, R. H. Advances in Polymer Science; Springer Verlag: New York, 1992; Vol. 102; p 47. (b) Schrock, R. R. Acc. Chem. Res. 1990, 23, 158. (c) Ivin, K. J. Olefin Metathesis, Academic Press: London, 1983.
51. Schleyer, P. v. R.; Williams, J. E.; Blanchard, K. R. J. Am. Chem. Soc. 1972, 94, 7723.
52. (a) Munk, P. Introduction to Macromolecular Science, John Wiley: New York, 1989.
53. (b) Stevens, M. P. Polymer Chemistry, an Introduction, 2nd ed.; Oxford University Press: Oxford, England, 1990.
54. The rigid bicyclic structure renders the β-hydrogens inaccessible for β-hydride elimination, thus reducing the rate of chain-transfer reactions.
55. Wiberg, K. B.; Hartley, W. J. J. Am. Chem. Soc. 1960, 82, 6375.
56. Further studies will be required to confirm the mechanism of chain propagation. Polymerization could also proceed via the ene reaction which has been found to occur in the dimerization of cyclopropenes bearing allylic hydrogens: Binger, P.; Buch, H. M. Top. Curr. Chem. 1988, 144, 137.
57. Weigert, F. J.; Baird, R. L.; Shapley, J. R. J. Am. Chem. Soc. 1970, 92, 6630. These authors found that several mono- and trialkyl-substituted cyclopropenes produce predominantly cyclodimers. However, 1,2-dimethylcyclopropene reacts under formation of a ring-opened polymer containing one carbon-carbon double bond per repeating unit.
58. (a) Binger, P.; Schuchardt, U. Chem. Ber. 1981, 114, 1649.
59. (b) Binger, P.; McMeeking, J.; Schuchardt, U. Chem. Ber. 1980, 113, 2372.
60. (c) Binger, P.; Büch, H. M.; Benn, R.; Mynott, R. Angew. Chem., Int. Ed. Engl. 1982, 21, 62.
61. (d) Büch, H. M.; Krüger, C. Acta Crystallogr., C 1984, 40, 28.
62. Syntheses of 3a - c was performed according to procedures described in: (a) Binger, P. Synthesis 1974, 190. (b) Nesmeyanova, O. A.; Rudashevskaya, T. Y.; Dyachenko, A. I.; Savilova, S. F.; Nesedov, O. M. Synthesis 1982, 296. These three-step monomer syntheses are suitable for laboratory preparations on a scale of up to several grams. The third reaction step is to some degree experimentally demanding and requires high purity starting materials. Different monomer syntheses with potential for scale up are required in order to improve the overall practicality. Other cyclopropene syntheses were described in: (c) Closs, G. L.; Gloss, L. E.; Böll, W. A. J. Am. Chem. Soc. 1963, 85, 3796.
63. Syntheses of 3a - c was performed according to procedures described in: (a) Binger, P. Synthesis 1974, 190. (b) Nesmeyanova, O. A.; Rudashevskaya, T. Y.; Dyachenko, A. I.; Savilova, S. F.; Nesedov, O. M. Synthesis 1982, 296. These three-step monomer syntheses are suitable for laboratory preparations on a scale of up to several grams. The third reaction step is to some degree experimentally demanding and requires high purity starting materials. Different monomer syntheses with potential for scale up are required in order to improve the overall practicality. Other cyclopropene syntheses were described in: (c) Closs, G. L.; Gloss, L. E.; Böll, W. A. J. Am. Chem. Soc. 1963, 85, 3796.
64. Syntheses of 3a - c was performed according to procedures described in: (a) Binger, P. Synthesis 1974, 190. (b) Nesmeyanova, O. A.; Rudashevskaya, T. Y.; Dyachenko, A. I.; Savilova, S. F.; Nesedov, O. M. Synthesis 1982, 296. These three-step monomer syntheses are suitable for laboratory preparations on a scale of up to several grams. The third reaction step is to some degree experimentally demanding and requires high purity starting materials. Different monomer syntheses with potential for scale up are required in order to improve the overall practicality. Other cyclopropene syntheses were described in: (c) Closs, G. L.; Gloss, L. E.; Böll, W. A. J. Am. Chem. Soc. 1963, 85, 3796.
65. 1H NMR spectroscopy in bromobenzene-ds at 80°C.
66. Polymer yields decrease when the initial mol ratio of monomer to catalyst is increased (Table 1) due to the unselective nature of the polymerization when catalyst 4 is used.
67. Relative number average molecular weights of the parts of poly-3bb′ and poly-3cc′ soluble in chlorobenzene at 20°C (between 60 and 90 wt %); calibration with polystyrene samples.
68. (a) Binger, P.; Muller, P.; Benn, R.; Mynott, R. Angew. Chem., Int. Ed. Engl. 1989, 28, 610.
69. (b) Johnson, L. K.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1993, 115, 8130.
70. (c) Nguyen, S. T.; Johnson, L. K.; Grubbs, R. H. J. Am. Chem. Soc. 1992, 114, 3974.
71. (d) Gagne, M. R.; Grubbs, R. H.; Feldman, J.; Ziller, J. W. Organometallics 1992, 11, 3933.
72. (e) Flatt, B. T.; Grubbs, R. H.; Blanski, R. L.; Calabrese, J. C.; Feldman, J. Organometallics 1994, 13, 2728.
73. (f) Li, R. T.; Nguyen, S. T.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1994, 116, 10032.
74. Maassarani, F.; Pfeffer, M.; Le Borgne, G.; Grandjean, D. Organometallics 1986, 5, 1511.
75. (a) Ketley, A. D.; Braatz, J. A. J. Chem. Soc., Chem. Commun. 1968, 959,
76. (b) Ketley, A. D.; Braatz, J. A.; Craig, J. J. Chem. Soc., Chem. Commun. 1970, 1117.
77. (c) Ahmad, M.; Bäckvall, J. E.; Nordberg, R. E.; Norin, T.; Strömberg, S. J. Chem. Soc., Chem. Commun. 1982, 321.
78. (d) Didier, W.; Bäckvall, J.-E.; Nordberg, R. E.; Norin, T. Organometallics 1985, 4, 1296.
79. (e) Blomberg, M. R. A.; Siegbahn, P. E. M.; Bäckvall, J.-E. J. Am. Chem. Soc. 1987, 109, 4450.
80. 1H NMR spectrum of the resulting ring-opened polymer shows the olefinic signal at δ 5.45. The signal due to the cyclopropane ring protons of poly-3a at δ 0.65-0.45 disappears after reaction with 4.
81. -25c are described in: (a) Byers, P. K.; Canty, A. J.; Traill, P. R.; Watson, A. A. J. Organomet. Chem. 1990, 390, 399. (b) Deeming, A. J.; Rothwell, I. P.; Hursthouse, M. B.; Backer-Dirks, J. D. J. J. Chem. Soc., Chem. Commun. 1979, 670. (c) Crociani, B.; Di Bianca, F.; Uguagliati, P.; Canovese, L.; Berton, A. J. Chem. Soc., Dalton Trans. 1991, 71.
82. -25c are described in: (a) Byers, P. K.; Canty, A. J.; Traill, P. R.; Watson, A. A. J. Organomet. Chem. 1990, 390, 399. (b) Deeming, A. J.; Rothwell, I. P.; Hursthouse, M. B.; Backer-Dirks, J. D. J. J. Chem. Soc., Chem. Commun. 1979, 670. (c) Crociani, B.; Di Bianca, F.; Uguagliati, P.; Canovese, L.; Berton, A. J. Chem. Soc., Dalton Trans. 1991, 71.
83. -25c are described in: (a) Byers, P. K.; Canty, A. J.; Traill, P. R.; Watson, A. A. J. Organomet. Chem. 1990, 390, 399. (b) Deeming, A. J.; Rothwell, I. P.; Hursthouse, M. B.; Backer-Dirks, J. D. J. J. Chem. Soc., Chem. Commun. 1979, 670. (c) Crociani, B.; Di Bianca, F.; Uguagliati, P.; Canovese, L.; Berton, A. J. Chem. Soc., Dalton Trans. 1991, 71.
84. Togni, A.; Rihs, G.; Pregosin, P. S.; Ammann, C. Helv. Chim. Acta 1990, 73, 723.
85. Similar to: von Matt, P.; Lloyd-Jones, G. C.; Minidis, A. B. E.; Pfaltz, A.; Macko, L.; Neuburger, M.; Zehnder, M.; Rüegger, H.; Pregosin, P. S. Helv. Chim. Acta 1995, 78, 265.
86. Many of the cyclopropene polymerizations of Table 2 were precipitation polymerizations. As a result, direct relationships between polymer molecular weights and initial mole ratios of monomer to catalyst or polymer yield and reaction time are difficult to establish.
87. Poly-3a,b samples (entries 7-14) are only partially soluble at 20°C in chlorobenzene.
88. Chain propagation is being driven by both the release of ring strain and the energy gained from converting a π-bond into a σ-bond.
89. 3 at 20 °C.
90. Barrett, A. G. M.; Kasdorf, K.; Tustin, G. J.: Williams, D. J. J. Chem. Soc., Chem. Commun. 1995, 1143.
91. (a) Kalinowski, H.-O.; Berger, S.; Braun, S. Carbon-13 NMR Spectroscopy, John Wiley: Chichester, England, 1988.
92. (b) DePuy, C. H.; Fünfschilling, P. C.; Andrist, A. H.; Olson, J. Am. Chem. Soc. 1977, 99, 6297.
93. 13C NMR shift difference for Me(cis) and Me(trans) is a result of the rigidity of the polymer structure. There is no rotation about the C-C bonds which are part of the three-membered rings.
94. 5 (of 8). Both Me*(c) (δ 21.7) and Me*(t) (δ 27.8) can be compared with the geminal methyl groups of 1,1,2-trimethylcyclopropane 6f (δ 19.5 and 27.4 in Figure 2) as they experience only two additional δ-effects. Me(t) at δ 29.3 and Me(c) at 17.4 of 8 are in almost the same environment as Me(trans) and Me (cis) of 7. (They differ slightly due to a difference in the shielding/deshielding effects induced by the neighboring terminal cyclopropane units.) (Matrix Presented)
95. 36b However these polycyclopentenes are 1,3-linked polymers in contrast to the present 1,2-linked polycyclopropenes and are not really suited as a model for discussing chain-end control as the exclusive mechanism of stereocontrol.
96. (b) Kelly, W. M.; Collins, S. Macromolecules 1994, 27, 4477.
97. 4a
98. 16a They are the predominant reaction products in addition to small amounts of cyclotrimers and cyclotetramers.
99. 2-carbons of the ethyl substituents show peaks (overlapped by resonances corresponding to the three-membered ring carbons) at δ 23.9-22.9 when they are cis to the polymer main chain (3b,c units) and signals at δ 36.7-36.2 when they are in a trans position (3b,t units).
100. 13C NMR signals are shifted upfield due to the γ-syn effect.
101. -1 (at 373 K).