Catalytic hydrogenolysis at low temperature and pressure of polyethylene and polypropylene to diesels or lower alkanes by a zirconium hydride supported on silica-alumina: A step toward polyolefin degradation by the microscopic reverse of Ziegler-Natta polymerization

Angewandte Chemie - International Edition

Volumn 37, Issue 6, 1998, Pages 806-810

  Dufaud, Véronique ^a   Basset, Jean Marie ^a  

^a CPE LYON   (France)

Author keywords

Depolymerizations; Hydrogenolysis; Polymerizations; Zirconium

Indexed keywords

EID: 0031949089     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3773(19980403)37:6<806::AID-ANIE806>3.0.CO;2-6     Document Type: Article

References (58)

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11. For olefin polymerization mechanism with conventional Ziegler-Natta catalysts, see a) P. Corradini in Comprehensive Polymer Science, Vol. 4 (Ed.: Sir G. Allen), Pergamon, Oxford, 1988, pp. 40; b) P. Cossee, J. Catal. 1964, 3, 80; c) E. J. Arlman, P. J. Cossee, Catal, 1964, 3, 99; d) H. Sinn, W. Kaminsky, Adv. Organomet. Chem. 1980, 18, 99. For olefin polymerization mechanism with metallocene catalysts, see e) P. G. Gassman, M. R. Callstrom, J. Am. Chem. Soc. 1987, 109, 7875; f) H. Sinn, W. Kaminsky, H.-J. Vollmer, R. Woldt, Angew. Chem. 1980, 92, 396; Angew. Chem. Int. Ed. Engl. 1980, 19, 390; g) R. F. Jordan, Adv. Organomet. Chem. 1991, 32, 325; h) T. J. Marks, Acc. Chem. Res. 1992, 25, 57; i) J. J. Eisch, A. M. Piotrowski, S. K. Brownstein, E. J. Gabe, F. L. Lee, J. Am. Chem. Soc. 1985, 107, 7219; j) R. F. Jordan, C. S. Bajgur, R. Willett, B. Scott, ibid. 1986, 108, 7410.
12. For olefin polymerization mechanism with conventional Ziegler-Natta catalysts, see a) P. Corradini in Comprehensive Polymer Science, Vol. 4 (Ed.: Sir G. Allen), Pergamon, Oxford, 1988, pp. 40; b) P. Cossee, J. Catal. 1964, 3, 80; c) E. J. Arlman, P. J. Cossee, Catal, 1964, 3, 99; d) H. Sinn, W. Kaminsky, Adv. Organomet. Chem. 1980, 18, 99. For olefin polymerization mechanism with metallocene catalysts, see e) P. G. Gassman, M. R. Callstrom, J. Am. Chem. Soc. 1987, 109, 7875; f) H. Sinn, W. Kaminsky, H.-J. Vollmer, R. Woldt, Angew. Chem. 1980, 92, 396; Angew. Chem. Int. Ed. Engl. 1980, 19, 390; g) R. F. Jordan, Adv. Organomet. Chem. 1991, 32, 325; h) T. J. Marks, Acc. Chem. Res. 1992, 25, 57; i) J. J. Eisch, A. M. Piotrowski, S. K. Brownstein, E. J. Gabe, F. L. Lee, J. Am. Chem. Soc. 1985, 107, 7219; j) R. F. Jordan, C. S. Bajgur, R. Willett, B. Scott, ibid. 1986, 108, 7410.
13. For olefin polymerization mechanism with conventional Ziegler-Natta catalysts, see a) P. Corradini in Comprehensive Polymer Science, Vol. 4 (Ed.: Sir G. Allen), Pergamon, Oxford, 1988, pp. 40; b) P. Cossee, J. Catal. 1964, 3, 80; c) E. J. Arlman, P. J. Cossee, Catal, 1964, 3, 99; d) H. Sinn, W. Kaminsky, Adv. Organomet. Chem. 1980, 18, 99. For olefin polymerization mechanism with metallocene catalysts, see e) P. G. Gassman, M. R. Callstrom, J. Am. Chem. Soc. 1987, 109, 7875; f) H. Sinn, W. Kaminsky, H.-J. Vollmer, R. Woldt, Angew. Chem. 1980, 92, 396; Angew. Chem. Int. Ed. Engl. 1980, 19, 390; g) R. F. Jordan, Adv. Organomet. Chem. 1991, 32, 325; h) T. J. Marks, Acc. Chem. Res. 1992, 25, 57; i) J. J. Eisch, A. M. Piotrowski, S. K. Brownstein, E. J. Gabe, F. L. Lee, J. Am. Chem. Soc. 1985, 107, 7219; j) R. F. Jordan, C. S. Bajgur, R. Willett, B. Scott, ibid. 1986, 108, 7410.
14. For olefin polymerization mechanism with conventional Ziegler-Natta catalysts, see a) P. Corradini in Comprehensive Polymer Science, Vol. 4 (Ed.: Sir G. Allen), Pergamon, Oxford, 1988, pp. 40; b) P. Cossee, J. Catal. 1964, 3, 80; c) E. J. Arlman, P. J. Cossee, Catal, 1964, 3, 99; d) H. Sinn, W. Kaminsky, Adv. Organomet. Chem. 1980, 18, 99. For olefin polymerization mechanism with metallocene catalysts, see e) P. G. Gassman, M. R. Callstrom, J. Am. Chem. Soc. 1987, 109, 7875; f) H. Sinn, W. Kaminsky, H.-J. Vollmer, R. Woldt, Angew. Chem. 1980, 92, 396; Angew. Chem. Int. Ed. Engl. 1980, 19, 390; g) R. F. Jordan, Adv. Organomet. Chem. 1991, 32, 325; h) T. J. Marks, Acc. Chem. Res. 1992, 25, 57; i) J. J. Eisch, A. M. Piotrowski, S. K. Brownstein, E. J. Gabe, F. L. Lee, J. Am. Chem. Soc. 1985, 107, 7219; j) R. F. Jordan, C. S. Bajgur, R. Willett, B. Scott, ibid. 1986, 108, 7410.
15. For olefin polymerization mechanism with conventional Ziegler-Natta catalysts, see a) P. Corradini in Comprehensive Polymer Science, Vol. 4 (Ed.: Sir G. Allen), Pergamon, Oxford, 1988, pp. 40; b) P. Cossee, J. Catal. 1964, 3, 80; c) E. J. Arlman, P. J. Cossee, Catal, 1964, 3, 99; d) H. Sinn, W. Kaminsky, Adv. Organomet. Chem. 1980, 18, 99. For olefin polymerization mechanism with metallocene catalysts, see e) P. G. Gassman, M. R. Callstrom, J. Am. Chem. Soc. 1987, 109, 7875; f) H. Sinn, W. Kaminsky, H.-J. Vollmer, R. Woldt, Angew. Chem. 1980, 92, 396; Angew. Chem. Int. Ed. Engl. 1980, 19, 390; g) R. F. Jordan, Adv. Organomet. Chem. 1991, 32, 325; h) T. J. Marks, Acc. Chem. Res. 1992, 25, 57; i) J. J. Eisch, A. M. Piotrowski, S. K. Brownstein, E. J. Gabe, F. L. Lee, J. Am. Chem. Soc. 1985, 107, 7219; j) R. F. Jordan, C. S. Bajgur, R. Willett, B. Scott, ibid. 1986, 108, 7410.
16. For olefin polymerization mechanism with conventional Ziegler-Natta catalysts, see a) P. Corradini in Comprehensive Polymer Science, Vol. 4 (Ed.: Sir G. Allen), Pergamon, Oxford, 1988, pp. 40; b) P. Cossee, J. Catal. 1964, 3, 80; c) E. J. Arlman, P. J. Cossee, Catal, 1964, 3, 99; d) H. Sinn, W. Kaminsky, Adv. Organomet. Chem. 1980, 18, 99. For olefin polymerization mechanism with metallocene catalysts, see e) P. G. Gassman, M. R. Callstrom, J. Am. Chem. Soc. 1987, 109, 7875; f) H. Sinn, W. Kaminsky, H.-J. Vollmer, R. Woldt, Angew. Chem. 1980, 92, 396; Angew. Chem. Int. Ed. Engl. 1980, 19, 390; g) R. F. Jordan, Adv. Organomet. Chem. 1991, 32, 325; h) T. J. Marks, Acc. Chem. Res. 1992, 25, 57; i) J. J. Eisch, A. M. Piotrowski, S. K. Brownstein, E. J. Gabe, F. L. Lee, J. Am. Chem. Soc. 1985, 107, 7219; j) R. F. Jordan, C. S. Bajgur, R. Willett, B. Scott, ibid. 1986, 108, 7410.
17. For olefin polymerization mechanism with conventional Ziegler-Natta catalysts, see a) P. Corradini in Comprehensive Polymer Science, Vol. 4 (Ed.: Sir G. Allen), Pergamon, Oxford, 1988, pp. 40; b) P. Cossee, J. Catal. 1964, 3, 80; c) E. J. Arlman, P. J. Cossee, Catal, 1964, 3, 99; d) H. Sinn, W. Kaminsky, Adv. Organomet. Chem. 1980, 18, 99. For olefin polymerization mechanism with metallocene catalysts, see e) P. G. Gassman, M. R. Callstrom, J. Am. Chem. Soc. 1987, 109, 7875; f) H. Sinn, W. Kaminsky, H.-J. Vollmer, R. Woldt, Angew. Chem. 1980, 92, 396; Angew. Chem. Int. Ed. Engl. 1980, 19, 390; g) R. F. Jordan, Adv. Organomet. Chem. 1991, 32, 325; h) T. J. Marks, Acc. Chem. Res. 1992, 25, 57; i) J. J. Eisch, A. M. Piotrowski, S. K. Brownstein, E. J. Gabe, F. L. Lee, J. Am. Chem. Soc. 1985, 107, 7219; j) R. F. Jordan, C. S. Bajgur, R. Willett, B. Scott, ibid. 1986, 108, 7410.
18. For olefin polymerization mechanism with conventional Ziegler-Natta catalysts, see a) P. Corradini in Comprehensive Polymer Science, Vol. 4 (Ed.: Sir G. Allen), Pergamon, Oxford, 1988, pp. 40; b) P. Cossee, J. Catal. 1964, 3, 80; c) E. J. Arlman, P. J. Cossee, Catal, 1964, 3, 99; d) H. Sinn, W. Kaminsky, Adv. Organomet. Chem. 1980, 18, 99. For olefin polymerization mechanism with metallocene catalysts, see e) P. G. Gassman, M. R. Callstrom, J. Am. Chem. Soc. 1987, 109, 7875; f) H. Sinn, W. Kaminsky, H.-J. Vollmer, R. Woldt, Angew. Chem. 1980, 92, 396; Angew. Chem. Int. Ed. Engl. 1980, 19, 390; g) R. F. Jordan, Adv. Organomet. Chem. 1991, 32, 325; h) T. J. Marks, Acc. Chem. Res. 1992, 25, 57; i) J. J. Eisch, A. M. Piotrowski, S. K. Brownstein, E. J. Gabe, F. L. Lee, J. Am. Chem. Soc. 1985, 107, 7219; j) R. F. Jordan, C. S. Bajgur, R. Willett, B. Scott, ibid. 1986, 108, 7410.
19. For olefin polymerization mechanism with conventional Ziegler-Natta catalysts, see a) P. Corradini in Comprehensive Polymer Science, Vol. 4 (Ed.: Sir G. Allen), Pergamon, Oxford, 1988, pp. 40; b) P. Cossee, J. Catal. 1964, 3, 80; c) E. J. Arlman, P. J. Cossee, Catal, 1964, 3, 99; d) H. Sinn, W. Kaminsky, Adv. Organomet. Chem. 1980, 18, 99. For olefin polymerization mechanism with metallocene catalysts, see e) P. G. Gassman, M. R. Callstrom, J. Am. Chem. Soc. 1987, 109, 7875; f) H. Sinn, W. Kaminsky, H.-J. Vollmer, R. Woldt, Angew. Chem. 1980, 92, 396; Angew. Chem. Int. Ed. Engl. 1980, 19, 390; g) R. F. Jordan, Adv. Organomet. Chem. 1991, 32, 325; h) T. J. Marks, Acc. Chem. Res. 1992, 25, 57; i) J. J. Eisch, A. M. Piotrowski, S. K. Brownstein, E. J. Gabe, F. L. Lee, J. Am. Chem. Soc. 1985, 107, 7219; j) R. F. Jordan, C. S. Bajgur, R. Willett, B. Scott, ibid. 1986, 108, 7410.
20. For olefin polymerization mechanism with conventional Ziegler-Natta catalysts, see a) P. Corradini in Comprehensive Polymer Science, Vol. 4 (Ed.: Sir G. Allen), Pergamon, Oxford, 1988, pp. 40; b) P. Cossee, J. Catal. 1964, 3, 80; c) E. J. Arlman, P. J. Cossee, Catal, 1964, 3, 99; d) H. Sinn, W. Kaminsky, Adv. Organomet. Chem. 1980, 18, 99. For olefin polymerization mechanism with metallocene catalysts, see e) P. G. Gassman, M. R. Callstrom, J. Am. Chem. Soc. 1987, 109, 7875; f) H. Sinn, W. Kaminsky, H.-J. Vollmer, R. Woldt, Angew. Chem. 1980, 92, 396; Angew. Chem. Int. Ed. Engl. 1980, 19, 390; g) R. F. Jordan, Adv. Organomet. Chem. 1991, 32, 325; h) T. J. Marks, Acc. Chem. Res. 1992, 25, 57; i) J. J. Eisch, A. M. Piotrowski, S. K. Brownstein, E. J. Gabe, F. L. Lee, J. Am. Chem. Soc. 1985, 107, 7219; j) R. F. Jordan, C. S. Bajgur, R. Willett, B. Scott, ibid. 1986, 108, 7410.
21. For olefin polymerization mechanism with conventional Ziegler-Natta catalysts, see a) P. Corradini in Comprehensive Polymer Science, Vol. 4 (Ed.: Sir G. Allen), Pergamon, Oxford, 1988, pp. 40; b) P. Cossee, J. Catal. 1964, 3, 80; c) E. J. Arlman, P. J. Cossee, Catal, 1964, 3, 99; d) H. Sinn, W. Kaminsky, Adv. Organomet. Chem. 1980, 18, 99. For olefin polymerization mechanism with metallocene catalysts, see e) P. G. Gassman, M. R. Callstrom, J. Am. Chem. Soc. 1987, 109, 7875; f) H. Sinn, W. Kaminsky, H.-J. Vollmer, R. Woldt, Angew. Chem. 1980, 92, 396; Angew. Chem. Int. Ed. Engl. 1980, 19, 390; g) R. F. Jordan, Adv. Organomet. Chem. 1991, 32, 325; h) T. J. Marks, Acc. Chem. Res. 1992, 25, 57; i) J. J. Eisch, A. M. Piotrowski, S. K. Brownstein, E. J. Gabe, F. L. Lee, J. Am. Chem. Soc. 1985, 107, 7219; j) R. F. Jordan, C. S. Bajgur, R. Willett, B. Scott, ibid. 1986, 108, 7410.
22. For β-methyl and β-alkyl elimination, see a) P. Watson, C. Roe, J. Am. Chem. Soc. 1982, 104, 6471; b) "Initiation of Polymerisation": P. L. Watson, T. Herskovitz, ACS Symp. Ser. 1983, 212, 459-479; c) W. Kaminsky, H. Luker, Makromol. Chem. Rapid Commun. 1984, 5, 225; d) P. L. Watson, G. W. Parshall, Acc. Res. 1985, 18, 51; e) E. Bunel, B. Burger, J. Bercaw, J. Am. Chem. Soc. 1988, 110, 976; f) L. Schock, T. J. Marks, ibid. 1988, 110, 7701; g) B. Burger, M. Thompson, D. Cotter, J. Bercaw, ibid. 1990, 112, 1566; h) J. Eshuis, Y. Tan, J. Teuben, J. Renkema, J. Mol. Catal 1990, 62, 277; i) L. Resconi, F. Piemontesi, G. Franciscono, L. Abis, T. Fiorani, J. Am. Chem. Soc. 1992, 114, 1025; j) J. J. Eshuis, Y. Y. Tan, A. Meetsma, J. H. Teuben, J. Renkema, G. G. Evens, Organometallics 1992, 11, 362; k) K. McNeill, R. A. Andersen, R. Bergman, J. Am. Chem. Soc. 1995, 117, 3625; l) A.D. Horton, Organometatlics 1996, 15, 2675; m) L. D'ornelas, S. Reyes, F. Quignard, A. Choplin, J.-M. Basset, Chem. Lett. 1993, 1931.
23. For β-methyl and β-alkyl elimination, see a) P. Watson, C. Roe, J. Am. Chem. Soc. 1982, 104, 6471; b) "Initiation of Polymerisation": P. L. Watson, T. Herskovitz, ACS Symp. Ser. 1983, 212, 459-479; c) W. Kaminsky, H. Luker, Makromol. Chem. Rapid Commun. 1984, 5, 225; d) P. L. Watson, G. W. Parshall, Acc. Res. 1985, 18, 51; e) E. Bunel, B. Burger, J. Bercaw, J. Am. Chem. Soc. 1988, 110, 976; f) L. Schock, T. J. Marks, ibid. 1988, 110, 7701; g) B. Burger, M. Thompson, D. Cotter, J. Bercaw, ibid. 1990, 112, 1566; h) J. Eshuis, Y. Tan, J. Teuben, J. Renkema, J. Mol. Catal 1990, 62, 277; i) L. Resconi, F. Piemontesi, G. Franciscono, L. Abis, T. Fiorani, J. Am. Chem. Soc. 1992, 114, 1025; j) J. J. Eshuis, Y. Y. Tan, A. Meetsma, J. H. Teuben, J. Renkema, G. G. Evens, Organometallics 1992, 11, 362; k) K. McNeill, R. A. Andersen, R. Bergman, J. Am. Chem. Soc. 1995, 117, 3625; l) A.D. Horton, Organometatlics 1996, 15, 2675; m) L. D'ornelas, S. Reyes, F. Quignard, A. Choplin, J.-M. Basset, Chem. Lett. 1993, 1931.
24. For β-methyl and β-alkyl elimination, see a) P. Watson, C. Roe, J. Am. Chem. Soc. 1982, 104, 6471; b) "Initiation of Polymerisation": P. L. Watson, T. Herskovitz, ACS Symp. Ser. 1983, 212, 459-479; c) W. Kaminsky, H. Luker, Makromol. Chem. Rapid Commun. 1984, 5, 225; d) P. L. Watson, G. W. Parshall, Acc. Res. 1985, 18, 51; e) E. Bunel, B. Burger, J. Bercaw, J. Am. Chem. Soc. 1988, 110, 976; f) L. Schock, T. J. Marks, ibid. 1988, 110, 7701; g) B. Burger, M. Thompson, D. Cotter, J. Bercaw, ibid. 1990, 112, 1566; h) J. Eshuis, Y. Tan, J. Teuben, J. Renkema, J. Mol. Catal 1990, 62, 277; i) L. Resconi, F. Piemontesi, G. Franciscono, L. Abis, T. Fiorani, J. Am. Chem. Soc. 1992, 114, 1025; j) J. J. Eshuis, Y. Y. Tan, A. Meetsma, J. H. Teuben, J. Renkema, G. G. Evens, Organometallics 1992, 11, 362; k) K. McNeill, R. A. Andersen, R. Bergman, J. Am. Chem. Soc. 1995, 117, 3625; l) A.D. Horton, Organometatlics 1996, 15, 2675; m) L. D'ornelas, S. Reyes, F. Quignard, A. Choplin, J.-M. Basset, Chem. Lett. 1993, 1931.
25. For β-methyl and β-alkyl elimination, see a) P. Watson, C. Roe, J. Am. Chem. Soc. 1982, 104, 6471; b) "Initiation of Polymerisation": P. L. Watson, T. Herskovitz, ACS Symp. Ser. 1983, 212, 459-479; c) W. Kaminsky, H. Luker, Makromol. Chem. Rapid Commun. 1984, 5, 225; d) P. L. Watson, G. W. Parshall, Acc. Res. 1985, 18, 51; e) E. Bunel, B. Burger, J. Bercaw, J. Am. Chem. Soc. 1988, 110, 976; f) L. Schock, T. J. Marks, ibid. 1988, 110, 7701; g) B. Burger, M. Thompson, D. Cotter, J. Bercaw, ibid. 1990, 112, 1566; h) J. Eshuis, Y. Tan, J. Teuben, J. Renkema, J. Mol. Catal 1990, 62, 277; i) L. Resconi, F. Piemontesi, G. Franciscono, L. Abis, T. Fiorani, J. Am. Chem. Soc. 1992, 114, 1025; j) J. J. Eshuis, Y. Y. Tan, A. Meetsma, J. H. Teuben, J. Renkema, G. G. Evens, Organometallics 1992, 11, 362; k) K. McNeill, R. A. Andersen, R. Bergman, J. Am. Chem. Soc. 1995, 117, 3625; l) A.D. Horton, Organometatlics 1996, 15, 2675; m) L. D'ornelas, S. Reyes, F. Quignard, A. Choplin, J.-M. Basset, Chem. Lett. 1993, 1931.
26. For β-methyl and β-alkyl elimination, see a) P. Watson, C. Roe, J. Am. Chem. Soc. 1982, 104, 6471; b) "Initiation of Polymerisation": P. L. Watson, T. Herskovitz, ACS Symp. Ser. 1983, 212, 459-479; c) W. Kaminsky, H. Luker, Makromol. Chem. Rapid Commun. 1984, 5, 225; d) P. L. Watson, G. W. Parshall, Acc. Res. 1985, 18, 51; e) E. Bunel, B. Burger, J. Bercaw, J. Am. Chem. Soc. 1988, 110, 976; f) L. Schock, T. J. Marks, ibid. 1988, 110, 7701; g) B. Burger, M. Thompson, D. Cotter, J. Bercaw, ibid. 1990, 112, 1566; h) J. Eshuis, Y. Tan, J. Teuben, J. Renkema, J. Mol. Catal 1990, 62, 277; i) L. Resconi, F. Piemontesi, G. Franciscono, L. Abis, T. Fiorani, J. Am. Chem. Soc. 1992, 114, 1025; j) J. J. Eshuis, Y. Y. Tan, A. Meetsma, J. H. Teuben, J. Renkema, G. G. Evens, Organometallics 1992, 11, 362; k) K. McNeill, R. A. Andersen, R. Bergman, J. Am. Chem. Soc. 1995, 117, 3625; l) A.D. Horton, Organometatlics 1996, 15, 2675; m) L. D'ornelas, S. Reyes, F. Quignard, A. Choplin, J.-M. Basset, Chem. Lett. 1993, 1931.
27. For β-methyl and β-alkyl elimination, see a) P. Watson, C. Roe, J. Am. Chem. Soc. 1982, 104, 6471; b) "Initiation of Polymerisation": P. L. Watson, T. Herskovitz, ACS Symp. Ser. 1983, 212, 459-479; c) W. Kaminsky, H. Luker, Makromol. Chem. Rapid Commun. 1984, 5, 225; d) P. L. Watson, G. W. Parshall, Acc. Res. 1985, 18, 51; e) E. Bunel, B. Burger, J. Bercaw, J. Am. Chem. Soc. 1988, 110, 976; f) L. Schock, T. J. Marks, ibid. 1988, 110, 7701; g) B. Burger, M. Thompson, D. Cotter, J. Bercaw, ibid. 1990, 112, 1566; h) J. Eshuis, Y. Tan, J. Teuben, J. Renkema, J. Mol. Catal 1990, 62, 277; i) L. Resconi, F. Piemontesi, G. Franciscono, L. Abis, T. Fiorani, J. Am. Chem. Soc. 1992, 114, 1025; j) J. J. Eshuis, Y. Y. Tan, A. Meetsma, J. H. Teuben, J. Renkema, G. G. Evens, Organometallics 1992, 11, 362; k) K. McNeill, R. A. Andersen, R. Bergman, J. Am. Chem. Soc. 1995, 117, 3625; l) A.D. Horton, Organometatlics 1996, 15, 2675; m) L. D'ornelas, S. Reyes, F. Quignard, A. Choplin, J.-M. Basset, Chem. Lett. 1993, 1931.
28. For β-methyl and β-alkyl elimination, see a) P. Watson, C. Roe, J. Am. Chem. Soc. 1982, 104, 6471; b) "Initiation of Polymerisation": P. L. Watson, T. Herskovitz, ACS Symp. Ser. 1983, 212, 459-479; c) W. Kaminsky, H. Luker, Makromol. Chem. Rapid Commun. 1984, 5, 225; d) P. L. Watson, G. W. Parshall, Acc. Res. 1985, 18, 51; e) E. Bunel, B. Burger, J. Bercaw, J. Am. Chem. Soc. 1988, 110, 976; f) L. Schock, T. J. Marks, ibid. 1988, 110, 7701; g) B. Burger, M. Thompson, D. Cotter, J. Bercaw, ibid. 1990, 112, 1566; h) J. Eshuis, Y. Tan, J. Teuben, J. Renkema, J. Mol. Catal 1990, 62, 277; i) L. Resconi, F. Piemontesi, G. Franciscono, L. Abis, T. Fiorani, J. Am. Chem. Soc. 1992, 114, 1025; j) J. J. Eshuis, Y. Y. Tan, A. Meetsma, J. H. Teuben, J. Renkema, G. G. Evens, Organometallics 1992, 11, 362; k) K. McNeill, R. A. Andersen, R. Bergman, J. Am. Chem. Soc. 1995, 117, 3625; l) A.D. Horton, Organometatlics 1996, 15, 2675; m) L. D'ornelas, S. Reyes, F. Quignard, A. Choplin, J.-M. Basset, Chem. Lett. 1993, 1931.
29. For β-methyl and β-alkyl elimination, see a) P. Watson, C. Roe, J. Am. Chem. Soc. 1982, 104, 6471; b) "Initiation of Polymerisation": P. L. Watson, T. Herskovitz, ACS Symp. Ser. 1983, 212, 459-479; c) W. Kaminsky, H. Luker, Makromol. Chem. Rapid Commun. 1984, 5, 225; d) P. L. Watson, G. W. Parshall, Acc. Res. 1985, 18, 51; e) E. Bunel, B. Burger, J. Bercaw, J. Am. Chem. Soc. 1988, 110, 976; f) L. Schock, T. J. Marks, ibid. 1988, 110, 7701; g) B. Burger, M. Thompson, D. Cotter, J. Bercaw, ibid. 1990, 112, 1566; h) J. Eshuis, Y. Tan, J. Teuben, J. Renkema, J. Mol. Catal 1990, 62, 277; i) L. Resconi, F. Piemontesi, G. Franciscono, L. Abis, T. Fiorani, J. Am. Chem. Soc. 1992, 114, 1025; j) J. J. Eshuis, Y. Y. Tan, A. Meetsma, J. H. Teuben, J. Renkema, G. G. Evens, Organometallics 1992, 11, 362; k) K. McNeill, R. A. Andersen, R. Bergman, J. Am. Chem. Soc. 1995, 117, 3625; l) A.D. Horton, Organometatlics 1996, 15, 2675; m) L. D'ornelas, S. Reyes, F. Quignard, A. Choplin, J.-M. Basset, Chem. Lett. 1993, 1931.
30. For β-methyl and β-alkyl elimination, see a) P. Watson, C. Roe, J. Am. Chem. Soc. 1982, 104, 6471; b) "Initiation of Polymerisation": P. L. Watson, T. Herskovitz, ACS Symp. Ser. 1983, 212, 459-479; c) W. Kaminsky, H. Luker, Makromol. Chem. Rapid Commun. 1984, 5, 225; d) P. L. Watson, G. W. Parshall, Acc. Res. 1985, 18, 51; e) E. Bunel, B. Burger, J. Bercaw, J. Am. Chem. Soc. 1988, 110, 976; f) L. Schock, T. J. Marks, ibid. 1988, 110, 7701; g) B. Burger, M. Thompson, D. Cotter, J. Bercaw, ibid. 1990, 112, 1566; h) J. Eshuis, Y. Tan, J. Teuben, J. Renkema, J. Mol. Catal 1990, 62, 277; i) L. Resconi, F. Piemontesi, G. Franciscono, L. Abis, T. Fiorani, J. Am. Chem. Soc. 1992, 114, 1025; j) J. J. Eshuis, Y. Y. Tan, A. Meetsma, J. H. Teuben, J. Renkema, G. G. Evens, Organometallics 1992, 11, 362; k) K. McNeill, R. A. Andersen, R. Bergman, J. Am. Chem. Soc. 1995, 117, 3625; l) A.D. Horton, Organometatlics 1996, 15, 2675; m) L. D'ornelas, S. Reyes, F. Quignard, A. Choplin, J.-M. Basset, Chem. Lett. 1993, 1931.
31. For β-methyl and β-alkyl elimination, see a) P. Watson, C. Roe, J. Am. Chem. Soc. 1982, 104, 6471; b) "Initiation of Polymerisation": P. L. Watson, T. Herskovitz, ACS Symp. Ser. 1983, 212, 459-479; c) W. Kaminsky, H. Luker, Makromol. Chem. Rapid Commun. 1984, 5, 225; d) P. L. Watson, G. W. Parshall, Acc. Res. 1985, 18, 51; e) E. Bunel, B. Burger, J. Bercaw, J. Am. Chem. Soc. 1988, 110, 976; f) L. Schock, T. J. Marks, ibid. 1988, 110, 7701; g) B. Burger, M. Thompson, D. Cotter, J. Bercaw, ibid. 1990, 112, 1566; h) J. Eshuis, Y. Tan, J. Teuben, J. Renkema, J. Mol. Catal 1990, 62, 277; i) L. Resconi, F. Piemontesi, G. Franciscono, L. Abis, T. Fiorani, J. Am. Chem. Soc. 1992, 114, 1025; j) J. J. Eshuis, Y. Y. Tan, A. Meetsma, J. H. Teuben, J. Renkema, G. G. Evens, Organometallics 1992, 11, 362; k) K. McNeill, R. A. Andersen, R. Bergman, J. Am. Chem. Soc. 1995, 117, 3625; l) A.D. Horton, Organometatlics 1996, 15, 2675; m) L. D'ornelas, S. Reyes, F. Quignard, A. Choplin, J.-M. Basset, Chem. Lett. 1993, 1931.
32. For β-methyl and β-alkyl elimination, see a) P. Watson, C. Roe, J. Am. Chem. Soc. 1982, 104, 6471; b) "Initiation of Polymerisation": P. L. Watson, T. Herskovitz, ACS Symp. Ser. 1983, 212, 459-479; c) W. Kaminsky, H. Luker, Makromol. Chem. Rapid Commun. 1984, 5, 225; d) P. L. Watson, G. W. Parshall, Acc. Res. 1985, 18, 51; e) E. Bunel, B. Burger, J. Bercaw, J. Am. Chem. Soc. 1988, 110, 976; f) L. Schock, T. J. Marks, ibid. 1988, 110, 7701; g) B. Burger, M. Thompson, D. Cotter, J. Bercaw, ibid. 1990, 112, 1566; h) J. Eshuis, Y. Tan, J. Teuben, J. Renkema, J. Mol. Catal 1990, 62, 277; i) L. Resconi, F. Piemontesi, G. Franciscono, L. Abis, T. Fiorani, J. Am. Chem. Soc. 1992, 114, 1025; j) J. J. Eshuis, Y. Y. Tan, A. Meetsma, J. H. Teuben, J. Renkema, G. G. Evens, Organometallics 1992, 11, 362; k) K. McNeill, R. A. Andersen, R. Bergman, J. Am. Chem. Soc. 1995, 117, 3625; l) A.D. Horton, Organometatlics 1996, 15, 2675; m) L. D'ornelas, S. Reyes, F. Quignard, A. Choplin, J.-M. Basset, Chem. Lett. 1993, 1931.
33. For β-methyl and β-alkyl elimination, see a) P. Watson, C. Roe, J. Am. Chem. Soc. 1982, 104, 6471; b) "Initiation of Polymerisation": P. L. Watson, T. Herskovitz, ACS Symp. Ser. 1983, 212, 459-479; c) W. Kaminsky, H. Luker, Makromol. Chem. Rapid Commun. 1984, 5, 225; d) P. L. Watson, G. W. Parshall, Acc. Res. 1985, 18, 51; e) E. Bunel, B. Burger, J. Bercaw, J. Am. Chem. Soc. 1988, 110, 976; f) L. Schock, T. J. Marks, ibid. 1988, 110, 7701; g) B. Burger, M. Thompson, D. Cotter, J. Bercaw, ibid. 1990, 112, 1566; h) J. Eshuis, Y. Tan, J. Teuben, J. Renkema, J. Mol. Catal 1990, 62, 277; i) L. Resconi, F. Piemontesi, G. Franciscono, L. Abis, T. Fiorani, J. Am. Chem. Soc. 1992, 114, 1025; j) J. J. Eshuis, Y. Y. Tan, A. Meetsma, J. H. Teuben, J. Renkema, G. G. Evens, Organometallics 1992, 11, 362; k) K. McNeill, R. A. Andersen, R. Bergman, J. Am. Chem. Soc. 1995, 117, 3625; l) A.D. Horton, Organometatlics 1996, 15, 2675; m) L. D'ornelas, S. Reyes, F. Quignard, A. Choplin, J.-M. Basset, Chem. Lett. 1993, 1931.
34. For β-methyl and β-alkyl elimination, see a) P. Watson, C. Roe, J. Am. Chem. Soc. 1982, 104, 6471; b) "Initiation of Polymerisation": P. L. Watson, T. Herskovitz, ACS Symp. Ser. 1983, 212, 459-479; c) W. Kaminsky, H. Luker, Makromol. Chem. Rapid Commun. 1984, 5, 225; d) P. L. Watson, G. W. Parshall, Acc. Res. 1985, 18, 51; e) E. Bunel, B. Burger, J. Bercaw, J. Am. Chem. Soc. 1988, 110, 976; f) L. Schock, T. J. Marks, ibid. 1988, 110, 7701; g) B. Burger, M. Thompson, D. Cotter, J. Bercaw, ibid. 1990, 112, 1566; h) J. Eshuis, Y. Tan, J. Teuben, J. Renkema, J. Mol. Catal 1990, 62, 277; i) L. Resconi, F. Piemontesi, G. Franciscono, L. Abis, T. Fiorani, J. Am. Chem. Soc. 1992, 114, 1025; j) J. J. Eshuis, Y. Y. Tan, A. Meetsma, J. H. Teuben, J. Renkema, G. G. Evens, Organometallics 1992, 11, 362; k) K. McNeill, R. A. Andersen, R. Bergman, J. Am. Chem. Soc. 1995, 117, 3625; l) A.D. Horton, Organometatlics 1996, 15, 2675; m) L. D'ornelas, S. Reyes, F. Quignard, A. Choplin, J.-M. Basset, Chem. Lett. 1993, 1931.
35. V. Dufaud, J.-M. Basset (CPE Lyon), XF-B 95 08 552, 1995, [Chem. Abstr. 1997, 126, 293772y].
36. F. Quignard, C. Lecuyer, C. Bougault, F. Lefevbre, A. Choplin, D. Olivier, J.-M. Basset, Inorg. Chem. 1992, 31, 928.
37. a) F. Quignard, A. Choplin, J.-M. Basset, J. Chem. Soc. Chem. Commun. 1991, 1589;
38. b) F. Quignard, C. Lecuyer, A. Choplin, D. Olivier, J.-M. Basset. J. Mol. Catal. 1992, 74, 353.
39. J. Corker, F. Lefebvre, C. Lécuyer, V. Dufaud, F. Quignard, A. Choplin, J. Evans, J.-M. Basset, Science 1996, 276, 966.
40. S. L. Scott, J.-M. Basset, J. Mol. Catal. 1994, 86, 5.
41. π, interaction between the oxygen lone pair orbitals and the Zr orbitals.
42. C. Lecuyer, F. Quignard, A. Choplin, D. Olivier, J.-M. Basset, Angew. Chem. 1991, 103, 1692; Angew. Chem. Int. Ed. Engl. 1991, 30, 1660.
43. C. Lecuyer, F. Quignard, A. Choplin, D. Olivier, J.-M. Basset, Angew. Chem. 1991, 103, 1692; Angew. Chem. Int. Ed. Engl. 1991, 30, 1660.
44. [7] includes the following elementary steps: 1) electrophilic activation of a C-H bond of the alkane by a highly electrophilic zirconium hydride on the surface by σ-bond metathesis. 2) β-alkyl migration with formation of an (alkyl)(olefin)zirconium complex, 3) hydrogenolysis of the alkylzirconium complex with liberation of an alkane and formation of a surface (hydride)(olefin)-zirconium complex, 4) insertion by the latter of the coordinated olefin into the Zr-H bond, and 5) hydrogenolysis of the new surface alkylzirconium species to give an alkane with regeneration of the electrophilic zirconium catalyst. No hydrogenolysis was observed with ethane owing to the lack of an alkyl group in the β-position.
45. For polyethylene and polypropylene IR data, see C. Pouchert in The Aldrich Library of Infrared Spectra, 1981, 3rd. ed.
46. The polymerization of ethylene or propylene with alumina-supported zirconium hydrides is well known; see, for example, a) A. M. Pyle, K. J. Jens, J. Mol. Catal. 1986, 38, 337; b) V. A. Zakharov, Y. A. Ryndin, ibid. 1989, 56, 183; c) J. P. Candlin, H. Thomas, Adv. Chem. Ser. 1976, 132, 212; d) Y. I. Yermakov, V. A. Zakharov in Coordination Polymerization (Ed.: J. C. Chien), Academic Press, New York, 1975, pp. 91; e) V. A. Zakharov, V. K. Dudchenko, A. I. Minkov, O. N. Efrimov, L. G. Khomyakova, V. P. Babenko, Y. I. Yermakov, Kinet. Catal. 1976, 17, 643; f) V. A. Zakharov, Y. I. Yermakov, Catal. Rev. Sci. Eng. 1979, 19, 67; g) L. E. Firment, J. Catal. 1983, 82, 196; h) P. J. Toscano, T. J. Marks, J. Am. Chem. Soc. 1985, 107, 653.
47. The polymerization of ethylene or propylene with alumina-supported zirconium hydrides is well known; see, for example, a) A. M. Pyle, K. J. Jens, J. Mol. Catal. 1986, 38, 337; b) V. A. Zakharov, Y. A. Ryndin, ibid. 1989, 56, 183; c) J. P. Candlin, H. Thomas, Adv. Chem. Ser. 1976, 132, 212; d) Y. I. Yermakov, V. A. Zakharov in Coordination Polymerization (Ed.: J. C. Chien), Academic Press, New York, 1975, pp. 91; e) V. A. Zakharov, V. K. Dudchenko, A. I. Minkov, O. N. Efrimov, L. G. Khomyakova, V. P. Babenko, Y. I. Yermakov, Kinet. Catal. 1976, 17, 643; f) V. A. Zakharov, Y. I. Yermakov, Catal. Rev. Sci. Eng. 1979, 19, 67; g) L. E. Firment, J. Catal. 1983, 82, 196; h) P. J. Toscano, T. J. Marks, J. Am. Chem. Soc. 1985, 107, 653.
48. The polymerization of ethylene or propylene with alumina-supported zirconium hydrides is well known; see, for example, a) A. M. Pyle, K. J. Jens, J. Mol. Catal. 1986, 38, 337; b) V. A. Zakharov, Y. A. Ryndin, ibid. 1989, 56, 183; c) J. P. Candlin, H. Thomas, Adv. Chem. Ser. 1976, 132, 212; d) Y. I. Yermakov, V. A. Zakharov in Coordination Polymerization (Ed.: J. C. Chien), Academic Press, New York, 1975, pp. 91; e) V. A. Zakharov, V. K. Dudchenko, A. I. Minkov, O. N. Efrimov, L. G. Khomyakova, V. P. Babenko, Y. I. Yermakov, Kinet. Catal. 1976, 17, 643; f) V. A. Zakharov, Y. I. Yermakov, Catal. Rev. Sci. Eng. 1979, 19, 67; g) L. E. Firment, J. Catal. 1983, 82, 196; h) P. J. Toscano, T. J. Marks, J. Am. Chem. Soc. 1985, 107, 653.
49. The polymerization of ethylene or propylene with alumina-supported zirconium hydrides is well known; see, for example, a) A. M. Pyle, K. J. Jens, J. Mol. Catal. 1986, 38, 337; b) V. A. Zakharov, Y. A. Ryndin, ibid. 1989, 56, 183; c) J. P. Candlin, H. Thomas, Adv. Chem. Ser. 1976, 132, 212; d) Y. I. Yermakov, V. A. Zakharov in Coordination Polymerization (Ed.: J. C. Chien), Academic Press, New York, 1975, pp. 91; e) V. A. Zakharov, V. K. Dudchenko, A. I. Minkov, O. N. Efrimov, L. G. Khomyakova, V. P. Babenko, Y. I. Yermakov, Kinet. Catal. 1976, 17, 643; f) V. A. Zakharov, Y. I. Yermakov, Catal. Rev. Sci. Eng. 1979, 19, 67; g) L. E. Firment, J. Catal. 1983, 82, 196; h) P. J. Toscano, T. J. Marks, J. Am. Chem. Soc. 1985, 107, 653.
50. The polymerization of ethylene or propylene with alumina-supported zirconium hydrides is well known; see, for example, a) A. M. Pyle, K. J. Jens, J. Mol. Catal. 1986, 38, 337; b) V. A. Zakharov, Y. A. Ryndin, ibid. 1989, 56, 183; c) J. P. Candlin, H. Thomas, Adv. Chem. Ser. 1976, 132, 212; d) Y. I. Yermakov, V. A. Zakharov in Coordination Polymerization (Ed.: J. C. Chien), Academic Press, New York, 1975, pp. 91; e) V. A. Zakharov, V. K. Dudchenko, A. I. Minkov, O. N. Efrimov, L. G. Khomyakova, V. P. Babenko, Y. I. Yermakov, Kinet. Catal. 1976, 17, 643; f) V. A. Zakharov, Y. I. Yermakov, Catal. Rev. Sci. Eng. 1979, 19, 67; g) L. E. Firment, J. Catal. 1983, 82, 196; h) P. J. Toscano, T. J. Marks, J. Am. Chem. Soc. 1985, 107, 653.
51. The polymerization of ethylene or propylene with alumina-supported zirconium hydrides is well known; see, for example, a) A. M. Pyle, K. J. Jens, J. Mol. Catal. 1986, 38, 337; b) V. A. Zakharov, Y. A. Ryndin, ibid. 1989, 56, 183; c) J. P. Candlin, H. Thomas, Adv. Chem. Ser. 1976, 132, 212; d) Y. I. Yermakov, V. A. Zakharov in Coordination Polymerization (Ed.: J. C. Chien), Academic Press, New York, 1975, pp. 91; e) V. A. Zakharov, V. K. Dudchenko, A. I. Minkov, O. N. Efrimov, L. G. Khomyakova, V. P. Babenko, Y. I. Yermakov, Kinet. Catal. 1976, 17, 643; f) V. A. Zakharov, Y. I. Yermakov, Catal. Rev. Sci. Eng. 1979, 19, 67; g) L. E. Firment, J. Catal. 1983, 82, 196; h) P. J. Toscano, T. J. Marks, J. Am. Chem. Soc. 1985, 107, 653.
52. The polymerization of ethylene or propylene with alumina-supported zirconium hydrides is well known; see, for example, a) A. M. Pyle, K. J. Jens, J. Mol. Catal. 1986, 38, 337; b) V. A. Zakharov, Y. A. Ryndin, ibid. 1989, 56, 183; c) J. P. Candlin, H. Thomas, Adv. Chem. Ser. 1976, 132, 212; d) Y. I. Yermakov, V. A. Zakharov in Coordination Polymerization (Ed.: J. C. Chien), Academic Press, New York, 1975, pp. 91; e) V. A. Zakharov, V. K. Dudchenko, A. I. Minkov, O. N. Efrimov, L. G. Khomyakova, V. P. Babenko, Y. I. Yermakov, Kinet. Catal. 1976, 17, 643; f) V. A. Zakharov, Y. I. Yermakov, Catal. Rev. Sci. Eng. 1979, 19, 67; g) L. E. Firment, J. Catal. 1983, 82, 196; h) P. J. Toscano, T. J. Marks, J. Am. Chem. Soc. 1985, 107, 653.
53. The polymerization of ethylene or propylene with alumina-supported zirconium hydrides is well known; see, for example, a) A. M. Pyle, K. J. Jens, J. Mol. Catal. 1986, 38, 337; b) V. A. Zakharov, Y. A. Ryndin, ibid. 1989, 56, 183; c) J. P. Candlin, H. Thomas, Adv. Chem. Ser. 1976, 132, 212; d) Y. I. Yermakov, V. A. Zakharov in Coordination Polymerization (Ed.: J. C. Chien), Academic Press, New York, 1975, pp. 91; e) V. A. Zakharov, V. K. Dudchenko, A. I. Minkov, O. N. Efrimov, L. G. Khomyakova, V. P. Babenko, Y. I. Yermakov, Kinet. Catal. 1976, 17, 643; f) V. A. Zakharov, Y. I. Yermakov, Catal. Rev. Sci. Eng. 1979, 19, 67; g) L. E. Firment, J. Catal. 1983, 82, 196; h) P. J. Toscano, T. J. Marks, J. Am. Chem. Soc. 1985, 107, 653.
54. S. Reyes, G. P. Niccolai, J.-M. Basset, unpublished results.
55. a) D. R. McAlister, D. K. Erwin, J. E. Bercaw, J. Am. Chem. Soc. 1978, 100, 5966;
56. b) J. E. Bercaw, Adv. Chem. Ser. 1978, 167, 136;
57. c) M. E. Thompson, S. M. Baxter, A. R. Bulls, B. J. Burger, M. C. Nolan, B. D. Santarsiero, W. P. Schaefer, J. E. Bercaw, J. Am. Chem. Soc. 1987, 109, 203.
58. S. A. King, J. Schwartz, Inorg. Chem. 1991, 30, 3771.