[en] The ring-opening metathesis polymerization (ROMP) of two optically active 2,3-dicarboalkoxynorbornadienes derived from (S)-(-)-2-methyl-1-butanol and (R)-(-)-2-butanol were carried out in the presence of the [RuCl2(P-cymene)](2) catalyst precursor activated by trimethylsilyldiazomethane (TMSD). H-1 and C-13 NMR analyses showed that a high degree of stereoregularity was achieved, and homonuclear proton-proton COSY spectroscopy indicated that the major trans fractions of the polymers were most likely isotactic, while the minor cis fractions were syndiotactic. Ring-opened metathesis polymers were also made from 2,3-dicarbomethoxynorbornadiene and exo,exo-2,3-dicarbomethoxy-5-norbornene. They were hydrogenated into the corresponding polynorbornanes using diimide. The NMR spectra of the reduced materials confirmed that the unsaturated parent polymers had an all-trans highly isotactic microstructure. A tentative mechanism involving arene loss, carbene formation, and monomer chelation is proposed to account for the observed stereoselectivities.
Disciplines :
Chemistry
Author, co-author :
Delaude, Lionel ; Université de Liège - ULiège > Chimie macromoléculaire et catalyse organique
Demonceau, Albert ; Université de Liège - ULiège > Chimie macromoléculaire et catalyse organique
Noels, Alfred ; Université de Liège - ULiège > Services généraux (Faculté des sciences) > Relations académiques et scientifiques (Sciences)
Language :
English
Title :
Probing the stereoselectivity of the ruthenium-catalyzed ring-opening metathesis polymerization of norbornene and norbornadiene diesters
Publication date :
2003
Journal title :
Macromolecules
ISSN :
0024-9297
eISSN :
1520-5835
Publisher :
Amer Chemical Soc, Washington, United States - District of Columbia
Ivin, K. J.; Mol, J. C. Olefm Metathesis and Metathesis Polymerization; Academic Press: San Diego, CA, 1997.
(a) Imamoglu, Y., Ed. Metathesis Polymerization of Olefins and Polymerization of Alkynes; NATO ASI Series C; Kluwer: Dordrecht, The Netherlands, 1998; Vol. 506.
(b) Khosravi, E.; Szyraanska-Buzar, T., Eds.; Ring Opening Metathesis Polymerisation and Related Chemistry; NATO Science Series II; Kluwer: Dordrecht, 2002; Vol 56.
(a) Schrock, R. R. Acc. Chem. Res. 1990, 23, 158-165.
(b) Trnak, T. M.; Grubbs, R. H. Acc. Chem. Res. 2001, 34, 18-29.
Hamilton, J. G. Polymer 1998, 39, 1669-1689.
(a) Ivin, K. J.; Laverty, D. T.; Rooney, J. J. Makromol. Chem. 1977, 178, 1545-1560.
(b) Ivin, K. J.; Laverty, D. T.; Rooney, J. J.; Watt, P. Reel. Trav. Chim. Pays-Bas 1977, 96, M54-M58.
(c) Ivin, K. J.; Lapienis, G.; Rooney, J. J. Chem. Commun. 1979, 1068-1070.
(d) Ivin, K. J.; Lapienis, G.; Rooney, J. J. Polymer 1980, 21, 436-443.
Ho, H. T.; Ivin, K. J.; Rooney, J. J. Makromol. Chem. 1982, 183, 1629-1646.
Steinhäusler, T.; Stelzer, F.; Zenkl, E. Polymer 1994, 35, 616-621.
Feast, W. J.; Gibson, V. C.; Ivin, K. J.; Kenwright, A. M.; Khosravi, E. J. Mol. Catal. 1994, 90, 87-99.
Sunaga, T.; Ivin, K. J.; Hofmeister, G. E.; Oskam, J. H.; Schrock, R. R. Macromolecules 1994, 27, 4043-4050.
O'Dell, R.; McConville, D. H.; Hofmeister, G. E.; Schrock, R. R. J. Am. Chem. Soc. 1994, 116, 3414-3423.
Hamilton, J. G.; Ivin, K. J.; Rooney, J. J. Br. Polym. J. 1984, 16, 21-33.
Al-Samak, B.; Amir-Ebrahimi, V.; Carvill, A. G.; Hamilton, J. G.; Rooney, J. J. Polym. Int. 1996, 41, 85-92.
Amir-Ebrahimi, V.; Corry, D. A. K.; Hamilton, J. G.; Rooney, J. J. J. Mol. Catal. A: Chem. 1998, 133, 115-122.
(a) Davies, G. R.; Hubbard, H. V. St A.; Ward, I. M.; Feast, W. J.; Gibson, V. C.; Khorasvi, E.; Marshall, E. L. Polymer 1995, 36, 235-243.
(b) Davies, G. R.; Almond, P. J.; Hubbard, H. V. St A.; Ward, I. M.; Feast, W. J.; Gibson, V. C.; Khosravi, E.; Marshall, E. L. Macromol. Symp. 1996, 102, 73-79.
Delaude, L.; Demonceau, A.; Noels, A. F. Macromolecules 1999, 32, 2091-2103.
For ease of comparison between polymers derived from various monomers, we have adopted a uniform numbering system based on norbornadiene. See Figures 4, 5, and 6 for assignments.
Stothers, J. B. Carbon-13 NMR Spectroscopy; Academic Press: London, 1972.
Bazan, G. C.; Schrock, R. R.; Cho, H.-N.; Gibson, V. C. Macromolecules 1991, 24, 4495-4502.
Kanaoka, S.; Grubbs, R. H. Macromolecules 1995, 28, 4707-4713.
Ivin, K. J.; Kress, J.; Osborn, J. A. Makromol. Chem. 1992, 193, 1695-1707.
Castner, K. F.; Calderon, N. J. Mol. Catal. 1982, 15, 47-59.
Ivin, K. J.; Kress, J.; Osborn, J. A. J. Mol. Catal 1988, 46, 351-358,
Ho, H. T.; Ivin, K. J.; Reddy, B. S. R.; Rooney, J. J. Eur. Polym. J. 1989, 25, 805-811.
Hamilton, J. G.; Rooney, J. J.; Snowden, D. G. Makromol. Chem. 1993, 194, 2907-2922.
Hamilton, J. G.; Rooney, J. J.; Snowden, D. G. Macromol. Chem. Phys. 1995, 196, 1031-1042.
Hillmyer, M. A.; Laredo, W. R.; Grubbs, R. H. Macromolecules 1995, 28, 6311-6316.
Harwood, H. J.; Russell, D. B.; Verthe, J. J. A,; Zymonas, J. Makromol. Chem. 1973, 163, 1-12.
Nang, T. D.; Katabe, Y.; Minoura, Y. Polymer 1976, 17, 117-120.
Chen, H. Y. J. Polym. Sci., Polym. Lett. Ed. 1977, 15, 271-275.
Tang, H. R.; McKee, M. L.; Stanbury, D. M. J. Am. Chem. Soc. 1995, 117, 8967-8973.
Miller, C. E. J. Chem. Educ. 1965, 42, 254-259.
Schrock, R. R.; Lee, J.-K.; O'Dell, R.; Oskam, J. H. Macromolecules 1995, 28, 5933-5940.
Amir-Ebrahimi, V.; Corry, D. A.; Hamilton, J. G.; Thompson, J. M.; Rooney, J. J. Macromolecules 2000, 33, 717-724.
Totland, K. M.; Boyd, T, J.; Lavoie, G. G.; Davis, W. M.; Schrock, R. R. Macromolecules 1996, 29, 6114-6125.
(a) Stumpf, A. W.; Saive, E.; Demonceau, A.; Noels, A. F. Chem. Commun. 1995, 1127-1128.
(b) Demonceau, A.; Stumpf, A. W.; Saive, E.; Noels, A. F. Macromolecules 1997, 30, 3127-3136.
Hafner, A.; Mühlebach, A.; van der Schaaf, P. A. Angew. Chem., Int. Ed. Engl. 1997, 36, 2121-2124.
Delaude, L.; Demonceau, A.; Noels, A. F. Chem. Commun. 2001, 986-987.
Reference 1, pp 252-254.
Hamilton, J. G.; Ivin, K. J.; McCann, G. M.; Rooney, J. J. Chem. Commun. 1984, 1379-1381.
Hérisson, J.-L.; Chauvin, Y. Makromol. Chem. 1971, 141, 161-176.
(a) Arnold, D. R.; Trecker, D, J.; Whipple, E. B. J. Am. Chem. Soc. 1965, 87, 2596-2602.
(b) Hamilton, J. G.; Ivin, K. J.; Rooney, J. J. J. Mol. Catal. 1985, 28, 255-278.
(c) Spanget-Larsen, J.; Gleiter, R. Tetrahedron 1983, 39, 3345-3350.