Title: Highly Efficient Ring-Opening Metathesis Polymerization (ROMP) Using New Ruthenium Catalysts Containing N-Heterocyclic Carbene Ligands
Abstract: Angewandte Chemie International EditionVolume 39, Issue 16 p. 2903-2906 Communication Highly Efficient Ring-Opening Metathesis Polymerization (ROMP) Using New Ruthenium Catalysts Containing N-Heterocyclic Carbene Ligands Christopher W. Bielawski, Christopher W. Bielawski Division of Chemistry and Chemical Engineering California Institute of Technology Pasadena, CA 91125 (USA) Fax: (+1) 626-564-9297Search for more papers by this authorRobert H. Grubbs Prof., Robert H. Grubbs Prof. [email protected] Division of Chemistry and Chemical Engineering California Institute of Technology Pasadena, CA 91125 (USA) Fax: (+1) 626-564-9297Search for more papers by this author Christopher W. Bielawski, Christopher W. Bielawski Division of Chemistry and Chemical Engineering California Institute of Technology Pasadena, CA 91125 (USA) Fax: (+1) 626-564-9297Search for more papers by this authorRobert H. Grubbs Prof., Robert H. Grubbs Prof. [email protected] Division of Chemistry and Chemical Engineering California Institute of Technology Pasadena, CA 91125 (USA) Fax: (+1) 626-564-9297Search for more papers by this author First published: 11 August 2000 https://doi.org/10.1002/1521-3773(20000818)39:16<2903::AID-ANIE2903>3.0.CO;2-QCitations: 531 C.B. is grateful to the National Science Foundation for a pre-doctoral fellowship. The authors thank Dr. Matthias Scholl for providing catalysts 4 a and 4 c. AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Abstract Up to one hundred thousand equivalents of a variety of low-strain cyclic olefins, such as cyclooctadiene, cyclooctene, and several functionalized and sterically hindered derivatives, were polymerized by using highly active ruthenium-based ring-opening metathesis polymerization (ROMP) catalysts [Eq. (1)]. Efficient syntheses of other polymeric structures were also accomplished. References 1a K. J. Ivin, J. C. Mol, Olefin Metathesis and Metathesis Polymerization, Academic Press, San Diego, CA, 1997; Google Scholar 1b D. S. Breslow, Prog. Polym. Sci. 1993, 18, 1141–1195. 10.1016/0079-6700(93)90012-2 CASWeb of Science®Google Scholar 2a R. R. Schrock, J. S. Murdzek, G. C. Bazan, J. Robbins, M. Dimare, M. O'Regan, J. Am. Chem. Soc. 1990, 112, 3875–3886; 10.1021/ja00166a023 CASWeb of Science®Google Scholar 2b R. R. Schrock, Acc. Chem. Res. 1990, 23, 158–165. 10.1021/ar00173a007 CASWeb of Science®Google Scholar 3 P. Schwab, R. H. Grubbs, J. W. Ziller, J. Am. Chem. Soc. 1996, 118, 100–110. 10.1021/ja952676d CASWeb of Science®Google Scholar 4 Initial investigations using RuCl3 salts as metathesis catalysts demonstrated the high functional group tolerance of ruthenium, see: Google Scholar 4a H. H. Thoi, K. J. Ivin, J. J. Rooney, J. Mol. Catal. 1982, 15, 245–270; 10.1016/0304-5102(82)80020-5 Web of Science®Google Scholar 4b B. M. Novak, R. H. Grubbs, J. Am. Chem. Soc. 1988, 110, 960–961. 10.1021/ja00211a043 CASWeb of Science®Google Scholar 5a J. Huang, E. D. Stevens, S. P. Nolan, J. L. Peterson, J. Am. Chem. Soc. 1999, 121, 2674–2678; 10.1021/ja9831352 CASWeb of Science®Google Scholar 5b M. Scholl, T. M. Trnka, J. P. Morgan, R. H. Grubbs, Tetrahedron Lett. 1999, 40, 2247–2250; 10.1016/S0040-4039(99)00217-8 CASWeb of Science®Google Scholar 5c T. Weskamp, F. J. Kohl, W. Hieringer, D. Gleich, W. A. Herrmann, Angew. Chem. 1999, 111, 2573–2576; Angew. Chem. Int. Ed. 1999, 38, 2416–2419; 10.1002/(SICI)1521-3757(19990816)111:16<2573::AID-ANGE2573>3.0.CO;2-A Google Scholar 5d J. Huang, H.-J. Schanz, E. D. Stevens, S. P. Nolan, Organometallics 1999, 18, 5375–5380. 10.1021/om990788y CASWeb of Science®Google Scholar 6 M. Scholl, S. Ding, C. W. Lee, R. H. Grubbs, Org. Lett. 1999, 1, 953–956. 10.1021/ol990909q CASPubMedWeb of Science®Google Scholar 7 A. K. Chatterjee, J. P. Morgan, M. Scholl, R. H. Grubbs, J. Am. Chem. Soc. 2000, 122, 3783–3784. 10.1021/ja9939744 CASWeb of Science®Google Scholar 8 L. Ackermann, A. Füstner, T. Weskamp, F. J. Kohl, W. A. Herrmann, Tetrahedron Lett. 1999, 40, 4787–4790. 10.1016/S0040-4039(99)00919-3 CASWeb of Science®Google Scholar 9 A. K. Chatterjee, R. H. Grubbs, Org. Lett. 1999, 1, 1751–1753. 10.1021/ol991023p CASPubMedWeb of Science®Google Scholar 10a T. Weskamp, W. C. Schattenmann, M. Spiegler, W. A. Herrmann, Angew. Chem. 1998, 110, 2631–2633; Angew. Chem. Int. Ed. 1998, 37, 2490–2493; corrigendum: 10.1002/(SICI)1521-3757(19980918)110:18<2631::AID-ANGE2631>3.0.CO;2-J Google Scholar 10b T. Weskamp, W. C. Schattenmann, M. Spiegler, W. A. Herrmann, Angew. Chem. 1999, 111, 277; Angew. Chem. Int. Ed. 1999, 38, 262. 10.1002/(SICI)1521-3757(19990816)111:16<2573::AID-ANGE2573>3.0.CO;2-A Google Scholar 11 It is well-established that complexes 3 and 4 are more active than 2 in ROMP.5c–d See also: U. Frenzel, T. Weskamp, F. J. Kohl, W. C. Schattenmann, O. Nuyken, W. A. Herrmann, J. Organomet. Chem. 1999, 586, 263–265. Google Scholar 12 The molybdenum catalyst 1 was purchased from Strem Chemicals and recrystallized from pentane at −40 °C prior to use. For the ROMP kinetics experiments, COD and CD2Cl2 were distilled from CaH2 and degassed prior to use. The ruthenium catalysts 3 and 4 were prepared as previously reported.5–7 All polymerizations were performed under an atmosphere of nitrogen. Google Scholar 13 A similar observation is obtained when comparing the ROMP activity of 2 (∼300 equiv COD per hour) and its dimethylvinyl carbene derivative (∼200 equiv COD per hour, catalyst structure not shown). Google Scholar 14 For a comprehensive study on phosphane effects in ruthenium-catalyzed olefin metathesis, see: E. L. Dias, S. T. Nguyen, R. H. Grubbs, J. Am. Chem. Soc. 1997, 119, 3887–3897. 10.1021/ja963136z CASWeb of Science®Google Scholar 15 For examples of polymerizing low-strain cyclic olefins using complex 1, see: P. Dounis, W. J. Feast, A. M. Kenwright, Polymer 1995, 36, 2787–2796. 10.1016/0032-3861(95)93658-9 CASWeb of Science®Google Scholar 16 Polymers of this type have been prepared by using 2, see: M. A. Hillmyer, W. R. Laredo, R. H. Grubbs, Macromolecules 1995, 28, 6311–6316. 10.1021/ma00122a043 CASWeb of Science®Google Scholar 17 Other functionalized cyclooctenes have been polymerized by using a cyclometalated aryloxy(chloro)neopentylidenenetungsten complex, see: Google Scholar 17a J.-L. Couturier, C. Paillet, M. Leconte, J.-M. Basset, K. Weiss, Angew. Chem. 1992, 104, 622–624; Angew. Chem. Int. Ed. Engl. 1992, 31, 628–631; 10.1002/ange.19921040521 CASGoogle Scholar 17b J.-L. Couturier, K. Tanaka, M. Leconte, J.-M. Basset, J. Ollivier, Angew. Chem. 1993, 105, 99; Angew. Chem. Int. Ed. Engl. 1993, 32, 112–115. 10.1002/ange.19931050123 CASGoogle Scholar 18a T. C. Chung, M. Chasmawala, Macromolecules 1992, 25, 5137–5144; 10.1021/ma00046a004 CASWeb of Science®Google Scholar 18b M. A. Hillmyer, S. T. Nguyen, R. H. Grubbs, Macromolecules 1997, 30, 718–721. 10.1021/ma961316n CASWeb of Science®Google Scholar 19 For a review on telechelic polymers, see: E. J. Goethals, Telechelic Polymers: Synthesis and Applications, CRC, Boca Raton, FL, 1989. Google Scholar 20 Chain transfer during the ROMP of other oxanorbornene derivatives has been observed to occur when initiated with RuCl3, see: M. B. France, R. H. Grubbs, D. V. McGrath, R. A. Paciello, Macromolecules 1993, 26, 4742–4747. 10.1021/ma00070a002 CASWeb of Science®Google Scholar 21a T. Viswanathan, F. Gomez, K. B. Wagener, J. Polym. Sci. Polym. Chem. 1994, 32, 2469–2477; 10.1002/pola.1994.080321308 CASWeb of Science®Google Scholar 21b H. Cramail, M. Fontanille, A. Soum, J. Mol. Catal. 1991, 65, 193–203. 10.1016/0304-5102(91)85096-K CASWeb of Science®Google Scholar 22a W. E. Crowe, J. P. Mitchell, V. C. Gibson, R. R. Schrock, Macromolecules 1990, 23, 3534–3536; 10.1021/ma00216a025 CASWeb of Science®Google Scholar 22b V. C. Gibson, T. Okada, Macromolecules 2000, 33, 655–656. 10.1021/ma990872p CASWeb of Science®Google Scholar 23 The 1,5-dimethyl-1,5-cyclooctadiene (6) employed in this study contained 1,6-dimethyl-1,5-cyclooctadiene (20 %) as an inseparable mixture. Google Scholar 24 The ethylene–propylene copolymer obtained was not “perfectly” alternating because of the impurity in 1,5-dimethyl-1,5-cyclooctadiene (6).25 We believe that if pure 6 was polymerized, the poly(isoprene) obtained would have perfectly alternating head-to-tail microstructure, since trisubstituted alkylidenes have not been observed to form. Thus, a perfectly alternating ethylene–propylene would be obtained after hydrogenation. Google Scholar 25 Z. Wu, R. H. Grubbs, Macromolecules 1995, 28, 3502–3508. 10.1021/ma00114a002 CASWeb of Science®Google Scholar Citing Literature Volume39, Issue16August 18, 2000Pages 2903-2906 This article also appears in:In Celebration of Robert H. Grubbs ReferencesRelatedInformation
Publication Year: 2000
Publication Date: 2000-08-18
Language: en
Type: article
Indexed In: ['crossref', 'pubmed']
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