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N-Heterocyclic Carbene Chelated Metal Complexes as Polymerization Catalysts

Published online by Cambridge University Press:  17 July 2013

Amer A. El-Batta*
Affiliation:
Department of Chemistry, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia
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Abstract

The synthesis of titanium and zirconium complexes ligated by bidentate “salicylaldimine-like” N-heterocyclic carbenes (NHCs) is reported. These complexes are rare examples of group IV transition metal NHC adducts. In the presence of methylaluminoxane these complexes are useful initiators for the polymerization of ethylene and the copolymerization of ethylene with norbornene and 1-octene. Linear high density polyethylene could be produced. The Ti complexes are also utilized to yield highly syndiotactic polystyrene.

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Articles
Copyright
Copyright © Materials Research Society 2013 

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References

REFERENCES

For the first reports of stable carbenes, see: (a)Igau, A., Grützmacher, H., Baceiredo, A., Bertrand, G., J. Am. Chem. Soc. 110, 64636466 (1988); (b) A. Igau, A. Baceiredo, G. Trinquier, G. Bertrand, Angew. Chem. Int. Ed. 28, 621 – 622 (1989); (c) For the first isolation of a stable NHC and its crystal structure analysis, see: A. J. Arduengo III, R. L. Harlow, M. Kline, J. Am. Chem. Soc. 113, 361 – 363 (1991).CrossRefGoogle Scholar
Lin, J. C. Y., Huang, R. T. W., Lee, C. S., Bhattacharyya, A., Hwang, W. S., Lin, I. J. B., Chem. Rev. 109, 35613598 (2009); (b)P. L. Arnold, I. J. Casely, Chem. Rev. 109, 3599 – 3611 (2009);(c) M. Poyatos, J. A. Mata, E. Peris, Chem. Rev. 109, 3677 – 3707 (2009); (d) O. Schuster, L. Yang, H. G. Raubenheimer, M. Albrecht, Chem. Rev. 109, 3445 – 3478 (2009); (e) S. Díez-González, N. Marion, S. P. Nolan, Chem. Rev. 109, 3612 – 3676 (2009); (f) B. Alcaide, P. Almendros, A. Luna, Chem. Rev. 109, 3817 – 3858 (2009); (g) G. C. Vougioukalakis, R. H. Grubbs, Chem. Rev. 110, 1746 – 1787 (2010).CrossRefGoogle Scholar
Green, J. C., Scurr, R. G., Arnold, P. L., Cloke, F. G. N., Chem. Commun. 1997, 1963 – 1964.CrossRefGoogle Scholar
(a)Waltman, A. W., Grubbs, R. H., Organometallics 23, 31053107 (2004); (b) A. W. Waltman, T. Ritter, R. H. Grubbs, Organometallics 25, 4238 – 4239 (2006).CrossRefGoogle Scholar
Younkin, T. R., Connor, E. F., Henderson, J. I., Friedrich, S. K., Grubbs, R. H., Bansleben, D. A., Science 287, 460462 (2000); (b) V. C. Gibson, S. Mastroianni, C. Newton, C. Redshaw, G. A. Solan, A. J. P. White, D. J. Williams, Dalton Trans. 2000, 1969 – 1971; (c) N. Matsukawa, S. Matsui, M. Mitani, J. Saito, K. Tsuru, N. Kashiwa, T. Fujita, J. Mol. Cat. A: Chemical 169, 99 – 104 (2001); (d) S. Matsui, M. Mitani, J. Saito, Y. Tohi, H. Makio, N. Matsukawa, Y. Takagi, T. Kazutaka, M. Nitabaru, T. Nakano, H. Tankaka, N. Kashiwa, T. Fujita, J. Am. Chem. Soc. 123, 6847 – 6856 (2001); (e) E. F. Connor, T. R. Younkin, J. I. Henderson, A. W. Waltman, R. H. Grubbs, Chem. Commun. 2003, 2272 – 2273; (f) H. Makio, T. Fujita, Bull. Chem. Soc. Jpn. 78, 52 – 66 (2005).CrossRefGoogle Scholar
El-Batta, A., Waltman, A. W., Grubbs, R. H., J. Organomet. Chem. 696, 24772481 (2011).CrossRefGoogle Scholar
Gibson, V. C., Spitzmesser, S. K., Chem. Rev. 103, 283315 (2003) and references therein.CrossRefGoogle Scholar
(a) For an example of ethylene/norbornene copolymerization catalyzed by a Ti complex similar to 2a, see: Y. Yoshida, J. Saito, M. Mitani, Y. Takagi, S. Matsui, S. Ishii, T. Nakano, N. Kashiwa, T. Fujita, Chem. Commun. 2002, 1298 – 1299; (b) For an example of α-olefin polymerization with Ti(sal)2 catalysts, see: J. Saito, M. Mitani, S. Matsui, N. Kashigawa, T. Fujita, Macromol. Rapid Commun. 21, 1333 – 1336 (2000). Google Scholar
Syndiotactic polymerization of propylene is well-documented for Ti and Zr bis-ligated sal complexes; see: (a)Tian, J., Coates, G. W., Angew. Chem., Int. Ed. 39, 36263629 (2000); (b) J. Tian, P. D. Hustad, G. W. Coates, J. Am. Chem. Soc. 123, 5134 – 5135 (2001); (c) P. D. Hustad, J. Tian, G. W. Coates, J. Am. Chem. Soc. 124, 3614 – 3621 (2002); (d) M. Mitani, R. Furuyama, J. Mohri, J. Saito, S. Ishii, H. Terao, N. Kashiwa, T. Fujita, J. Am. Chem. Soc. 124, 7888 – 7889 (2002).3.0.CO;2-U>CrossRefGoogle Scholar