Cobalt-Complex-Catalyzed Copolymerization of Ethylene with 2-Aryl-1-methylenecyclopropanes
Daisuke Takeuchi Dr.
Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan, Fax: (+81) 45-924-5224
Search for more papers by this authorKouhei Anada
Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan, Fax: (+81) 45-924-5224
Search for more papers by this authorKohtaro Osakada Prof. Dr.
Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan, Fax: (+81) 45-924-5224
Search for more papers by this authorDaisuke Takeuchi Dr.
Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan, Fax: (+81) 45-924-5224
Search for more papers by this authorKouhei Anada
Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan, Fax: (+81) 45-924-5224
Search for more papers by this authorKohtaro Osakada Prof. Dr.
Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan, Fax: (+81) 45-924-5224
Search for more papers by this authorGraphical Abstract
The importance of tolerance: A Cobalt complex with bis(imino)pyridine ligand promotes the alternating copolymerization of ethylene with 2-aryl-1-methylenecyclopropanes to give polymers with regulated C4 repeating units that have a three-membered ring (see scheme). The polymerization is tolerant of functional groups on the three-membered ring such as methoxy and chloro groups.
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References
- 1
- 1aS. Mecking, L. K. Johnson, L. Wang, M. Brookhart, J. Am. Chem. Soc. 1998, 120, 888–899;
- 1bE. Drent, R. van Dijk, R. van Ginkel, B. van Oort, R. I. Pugh, Chem. Commun. 2002, 744–745.
- 2
- 2aT. R. Younkin, E. F. Connor, J. I. Henderson, S. K. Friedrich, R. H. Grubbs, D. A. Bansleben, Science 2000, 287, 460–462;
- 2bG. M. Benedikt, E. Elce, B. L. Goodall, H. A. Kalamarides, L. H. McIntosh III, L. F. Rhodes, K. T. Selvy, C. Andes, K. Oyler, A. Sen, Macromolecules 2002, 35, 8978–8988.
- 3
- 3aH. Yasuda, M. Furo, H. Yamamoto, A. Nakamura, S. Miyake, N. Kibino, Macromolecules 1992, 25, 5115–5116;
- 3bH. Frauenrath, S. Balk, H. Keul, H. Höcker, Macromol. Rapid Commun. 2001, 22, 1147–1151.
- 4
- 4aT. Miyatake, K. Mizunuma, M. Kakugo, Makromol. Chem. Macromol. Symp. 1993, 66, 203–214;
- 4bT. Uozumi, K. Miyazawa, T. Sano, K. Soga, Macromol. Rapid Commun. 1997, 18, 883–889;
- 4cM. K. Leclerc, R. M. Waymouth, Angew. Chem. 1998, 110, 964–967;
10.1002/(SICI)1521-3757(19980403)110:7<964::AID-ANGE964>3.0.CO;2-T Google ScholarAngew. Chem. Int. Ed. 1998, 37, 922–925.10.1002/(SICI)1521-3773(19980420)37:7<922::AID-ANIE922>3.0.CO;2-G PubMed Web of Science® Google Scholar
- 5
- 5aW. Kaminsky, I. Beulich, M. Arndt-Rosenau, Macromol. Symp. 2001, 173, 211–225;
- 5bJ. Kiesewetter, W. Kaminsky, Chem. Eur. J. 2003, 9, 1750–1758;
- 5cA. L. McKnight, R. M. Waymouth, Macromolecules 1999, 32, 2816–2825.
- 6Polymerization of methylenecyclopropanes by Pd and Ni complexes.
- 6aD. Takeuchi, S. Kim, K. Osakada, Angew. Chem. 2001, 113, 2757–2760;
10.1002/1521-3757(20010716)113:14<2757::AID-ANGE2757>3.0.CO;2-# Google ScholarAngew. Chem. Int. Ed. 2001, 40, 2685–2688;10.1002/1521-3773(20010716)40:14<2685::AID-ANIE2685>3.0.CO;2-9 CAS PubMed Web of Science® Google Scholar
- 6bD. Takeuchi, K. Osakada, Chem. Commun. 2002, 646–647;
- 6cD. Takeuchi, K. Anada, K. Osakada, Macromolecules 2002, 35, 9628–9633.
- 7Copolymerization of methylenecyclopropanes with ethylene by early transition metal complexes.
- 7aL. Jia, X. Yang, A. M. Seyam, I. D. L. Albert, P.-F. Fu, S. Yang, T. J. Marks, J. Am. Chem. Soc. 1996, 118, 7900–7913;
- 7bT. R. Jensen, T. J. Marks, Macromolecules 2003, 36, 1775–1778.
- 8
- 8aB. L. Small, M. Brookhart, A. M. A. Bennett, J. Am. Chem. Soc. 1998, 120, 4049–4050;
- 8bG. J. P. Britovsek, V. C. Gibson, B. S. Kimberley, P. J. Maddox, S. J. McTavish, G. A. Solan, A. J. P. White, D. J. Williams, Chem. Commun. 1998, 849–850;
- 8cV. C. Gibson, M. J. Humphries, K. P. Tellmann, D. F. Wass, A. J. P. White, D. J. Williams, Chem. Commun. 2001, 2252–2253;
- 8dT. M. Kooistra, Q. Knijnenburg, J. M. M. Smits, A. D. Horton, P. H. M. Budzelaar, A. W. Gal, Angew. Chem. 2001, 113, 4855–4858;
10.1002/1521-3757(20011217)113:24<4855::AID-ANGE4855>3.0.CO;2-9 Google ScholarAngew. Chem. Int. Ed. 2001, 40, 4719–4722.10.1002/1521-3773(20011217)40:24<4719::AID-ANIE4719>3.0.CO;2-O CAS PubMed Web of Science® Google Scholar
- 9
- 9aB. L. Small, Organometallics 2003, 22, 3178–3183;
- 9bF. Pelascini, F. Peruch, P. J. Lutz, M. Wesolek, J. Kress, Macromol. Rapid Commun. 2003, 24, 768–771.
- 10Re-addition of 1 to the reaction mixture after consumption of the initially charged monomer (M̄n=8300, M̄w/M̄n=1.16) induces the polymerization to afford a product with an increased molecular weight and a narrow molecular weight distribution (M̄n=26 000, M̄w/M̄n=1.14); this result also indicates that the living polymerization is efficient. A slightly lower efficiency of the initiation than the ideal living polymerization is ascribed to slow or insufficient activation of the Co complex by MMAO. See also: P. Mehrkhodavandi, R. R. Schrock, L. L. Pryor, Organometallics 2003, 22, 4569–4583.
- 11Polymerization of methylenecyclopropane catalyzed by Zr and Ni complexes is proposed to involve the 1,2-insertion of the monomer into the MC σ bond (See refs [6b] and [7]). The 1,2-insertion of monomer is also supported by an end functionalization experiment.
- 12Recent papers on ethylene polymerization by Co catalyst (Ref [8c,d]) suggested that the CoIII complex is most likely the active species in the reaction.
- 13r2=k2,2/k2,ethylene and rethylene=kethylene,ethylene/kethylene,2, in which k2,2 and k2,ethylene denote the rate constants for the insertion reactions of 2 and ethylene into the CoC bond of CoCH2CCH2CH(C6H4OMe-4), respectively.
