Kinetic control and multiple mechanisms for C-H bond activation by a Zr=N complex

Angewandte Chemie - International Edition

Volumn 46, Issue 29, 2007, Pages 5580-5582

  Hoyt, Helen M ^a   Bergman, Robert G ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

C H activation; Hydrocarbons; Isotope effects; Reaction mechanisms; Zirconium

Indexed keywords

ADDITION REACTIONS; COMPLEXATION; HYDROCARBONS; ZIRCONIUM;

C-H ACTIVATION; ISOTOPE EFFECTS; REACTION MECHANISMS;

CHEMICAL BONDS;

CARBON; HYDROGEN; NITROGEN; ORGANOMETALLIC COMPOUND; ZIRCONIUM;

ARTICLE; CHEMICAL STRUCTURE; CHEMISTRY; KINETICS; SYNTHESIS;

CARBON; HYDROGEN; KINETICS; MOLECULAR STRUCTURE; NITROGEN; ORGANOMETALLIC COMPOUNDS; ZIRCONIUM;

EID: 34547161193     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200701816     Document Type: Article

References (38)

1. a) P. J Walsh, F. J. Hollander, R. G. Bergman, J. Am. Chem. Soc. 1988, 110, 8729;
2. b) P. J. Walsh, F. J. Hollander, R. G. Bergman, Organometallics 1993, 12, 3705;
3. c) S. Y. Lee, R. G. Bergman, J. Am. Chem. Soc. 1995, 117, 5877;
4. d) A. P. Duncan, R. G. Bergman, Chem. Rec. 2002, 2, 431;
5. e) H. M. Hoyt, F. E. Michael, R. G. Bergman, J. Am. Chem. Soc. 2004, 126, 1018;
6. f) C. C. Cummins, S. M. Baxter, P. T. Wolczanski, J. Am. Chem. Soc. 1988, 110, 8731;
7. g) C. C. Cummins, C. P. Schaller, G. D. Van Duyne, P. T. Wolczanski, A. W. E. Chan, R. Hoffmann, J. Am. Chem. Soc. 1991, 113, 2985;
8. h) C. P. Schaller, P. T. Wolczanski, Inorg. Chem. 1993, 32, 131;
9. i) J. de With, A. D. Horton, Angew. Chem. 1993, 105, 958;
10. Angew. Chem. Int. Ed. Engl. 1993, 32, 903;
11. j) J. L. Bennett, P. T. Wolczanski, J. Am. Chem. Soc. 1994, 116, 2197;
12. k) C. P. Schaller, J. B. Bonanno, P. T. Wolczanski, J. Am. Chem. Soc. 1994, 116, 2179;
13. l) C. P. Schaller, C. C. Cummins, P. T. Wolczanski, J. Am. Chem. Soc. 1996, 118, 591;
14. m) J. L. Bennett, P. T. Wolczanski, J. Am. Chem. Soc. 1997, 119, 10696;
15. n) D. F. Schafer, II, P. T. Wolczanski, J. Am. Chem. Soc. 1998, 120, 4881;
16. o) P. Royo, J. Sanchez-Nieves, J. Organomet. Chem. 2000, 597, 61.
17. Activation of HC≡CR: a) R. E. Blake, Jr., D. M. Antonelli, L. M. Henling, W. P. Schaefer, K. I. Hardcastle, J. E. Bercaw, Organometallics 1998, 17, 718;
18. b) J. L. Poise, R. A. Andersen, R. G. Bergman, J. Am. Chem. Soc. 1998, 120, 13405.
19. a) H. van der Heijden, B. Hessen, J. Chem. Soc. Chem. Commun. 1995, 145;
20. b) M. P. Coles, V. C. Gibson, W. Clegg, M. R. J. Elsegood, P.A. Porelli, Chem. Commun. 1996, 1963;
21. c) J. Cheon, D. M. Rogers, G. S. Girolami, J. Am. Chem. Soc. 1997, 119, 6804;
22. d) C. B. Pamplin, P. Legzdins, Acc. Chem. Res. 2003, 36, 223, and references therein;
23. e) K. Wada, C. B. Pamplin, P. Legzdins, B. O. Patrick, I. Tsyba, R. Bau, J. Am. Chem. Soc. 2003, 125, 7035;
24. f) I. J. Blackmore, P. Legzdins, Organometallics 2005, 24, 4088;
25. g) J. Y. K. Tsang, M. S. A. Buschhaus, P. Legzdins, B. O. Patrick, Organometallics 2006, 25, 4215.
26. a) B. C. Bailey, H. Fan, E. W. Baum, J. C. Huffman, M. Baik, D.J. Mindiola, J. Am. Chem. Soc. 2005, 127, 16016;
27. b) B. C. Bailey, J. C. Huffman, D. J. Mindiola, J. Am. Chem. Soc. 2007, 129, 5302.
28. Activation of HC≡CR: J. L. Poise, R. A. Andersen, R. G. Bergman, J. Am. Chem. Soc. 1995, 117, 5393.
29. a) R. L. Zuckerman, S. W. Krska, R. G. Bergman, J. Am. Chem. Soc. 2000, 122, 751;
30. [8];
31. [8]
32. 4.
33. See the Supporting Information for further details.
34. a) Product 3j slowly extrudes n-pentane at 45°C.
35. b) The kinetic selectivity for n-pentane remained constant up to 50% conversion,
36. c) KIE measured at 20% conversion.
37. a) T. R. Cundari, T. R. Klinckman, P. T. Wolczanski, J. Am. Chem. Soc. 2002, 124, 1481;
38. b) L. M. Slaughter, P. T. Wolczanski, T. R. Klinckman, T. R. Cundari, J. Am. Chem. Soc. 2000, 122, 7953.