Carbon-oxygen bond cleavage with η9,η5- bis(indenyl)zirconium sandwich complexes

Journal of the American Chemical Society

Volumn 128, Issue 51, 2006, Pages 16600-16612

  Bradley, Christopher A ^a   Veiros, Luis F ^b   Pun, Doris ^a   Lobkovsky, Emil ^a   Keresztes, Ivan ^a   Chírik, Paul J ^a  

^a Department of Obstetrics Gynecology   (United States)

^b INSTITUTO SUPERIOR TÉCNICO   (Portugal)

Author keywords

[No Author keywords available]

Indexed keywords

ALKOXIDE ELIMINATION; ALKYL HYDRIDES; HAPTOTROPIC REARRANGEMENT; THERMOLYSIS;

ACTIVATION ANALYSIS; CHEMICAL BONDS; COMPLEXATION; CRYSTALLOGRAPHY; OLEFINS; THERMOANALYSIS;

ZIRCONIUM COMPOUNDS;

ALKYL ETHER; BUTYRIC ACID; CARBON; ETA5,ETA5 BIS(INDENYL)ZIRCONIUM ETHYLENE DERIVATIVE; ETA9,ETA5 BIS(INDENYL)ZIRCONIUM DERIVATIVE; ETHER; HYDROGEN; OXYGEN; PRASEODYMIUM; TETRAHYDROFOLIC ACID; UNCLASSIFIED DRUG; ZIRCONIUM DERIVATIVE; ZIRCONOCENE;

ARTICLE; BINDING KINETICS; CHEMICAL BINDING; COMPLEX FORMATION; CRYSTALLOGRAPHY; ISOTOPE LABELING; OXIDATION REDUCTION REACTION; STRUCTURE ANALYSIS;

CARBON; ESTERS; KINETICS; MAGNETIC RESONANCE SPECTROSCOPY; MODELS, CHEMICAL; MODELS, MOLECULAR; MOLECULAR CONFORMATION; ORGANOMETALLIC COMPOUNDS; OXYGEN; SENSITIVITY AND SPECIFICITY; STEREOISOMERISM; ZIRCONIUM;

EID: 33845959445     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja065456g     Document Type: Article

References (50)

1. For a recent review, see: Titanium and Zirconium in Organic Synthesis: Marek, I., Ed.; Wiley-VCH: Weinheim, 2002.
2. (a) Pool, J. A.; Chirik, P. J. Can. J. Chem. 2005, 83, 286.
3. (b) Fryzuk, M. D.; Johnson, S. A. Coord. Chem. Rev. 2000, 200, 379.
4. (a) Negishi, E.-I.; Takahashi, T. Acc. Chem. Res. 1994, 27, 124.
5. (b) Rosenthal, U.; Pellny, P.-M.; Kirchbauer, F. G.; Burkalov, V. V. Acc. Chem. Res. 2000, 33, 119.
6. (a) Gambarotta, S.; Scott, J. Angew. Chem., Int. Ed. 2004, 43, 5298.
7. (b) Fryzuk, M. D. Chem. Rec. 2003, 3, 2.
8. For observation of bis(cyclopentadienyl)titanium sandwich complexes in solution see: (a) Bercaw, J. E.; Brintzinger, H. H. J. Am. Chem. Soc. 1971, 93, 2045.
9. (b) Bercaw, J. E. J. Am. Chem. Soc. 1974, 96, 5087.
10. (c) deWolf, J. M.; Blaauw, R.; Meetsma, A.; Teuben, J. H.; Gyepes, R.; Varga, V.; Mach, K.; Veldman, N.; Spek, A. L. Organometallics 1996, 15, 4977.
11. (d) Hanna, T. E.; Keresztes, I.; Lobkovsky, E.; Bernskoetter, W. H.; Chirik, P. J. Organometallics 2004, 23, 3448.
12. Hitchcock, P. B.; Kerton, F.; Lawless, G. A. J. Am. Chem. Soc. 1998, 120, 10264.
13. Lukesová, L.; Horácek, M.; Stepnicka, P.; Fejfarová, K.; Gyepes, R.; Cisorová, I.; Kubista, J.; Mach, K. J. Organomet. Chem. 2002, 663, 134.
14. Hanna, T. E.; Lobkovsky, E.; Chirik, P. J. J. Am. Chem. Soc. 2004, 126, 14688.
15. Hanna, T. E.; Lobkovsky, E.; Chirik, P. J. J. Am. Chem. Soc. 2006, 128, 6018.
16. Horácek, M.; Stepnicka, P.; Kubista, J.; Fejfarová, K.; Gyepes, R.; Mach, K. Organometallics 2003, 22, 861.
17. Bradley, C. A.; Lobkovsky, E.; Chirik, P. J. J. Am. Chem. Soc. 2003, 125, 8110.
18. Bradley, C. A.; Keresztes, I.; Lobkovsky, E.; Young, V. G.; Chirik, P. J. J. Am. Chem. Soc. 2004, 126, 16937.
19. Veiros, L. F. Chem.-Eur. J. 2005, 11, 2505.
20. For a review on indenyl hapticity, see: Calhorda, M. J.; Romão, C. C.; Veiros, L. F. Chem.-Eur. J. 2002, 8, 868.
21. For recent examples of accessing low-valent early transition metals by dissociation of a ligand, see: (a) Korobkov, I.; Arunachalampillai, A.; Gambarotta, S. Organometallics 2004, 23, 6248.
22. (b) Korobkov, I.; Gambarotta, S.; Yap, G. P. A. Angew. Chem., Int. Ed. 2003, 42, 814.
23. (c) Evans, W. J.; Davis, B. L. Chem. Rev. 2002, 102, 2119.
24. (d) Diaconescu, P.; Arnold, P. L.; Baker, T.; Mindiola, D. J.; Cummins, C. C. J. Am. Chem. Soc. 2000, 12, 6108.
25. (e) Tsai, Y.-C.; Johnson, M. A.; Mindiola, D. J.; Cummins, C. C.; Klooster, W. T.; Koetzle, T. F. J. Am. Chem. Soc. 1999, 121, 10426.
26. Veiros, L. F. Organometallics 2006, 25, 2266.
27. Bradley, C. A.; Kerestzes, I.; Lobkvosky, E.; Chirik, P. J. J. Am. Chem. Soc. 2005, 127, 10291.
28. Veiros, L. F. Organometallics 2006, 25, 4698.
29. For an example of a crystallographically characterized base-free ansa-zirconocene alkyne complex, see: Lefeber, C.; Baumann, W.; Tillack, A.; Kempe, R.; Görls, H.; Rosenthal, U. Organometallics 1996, 15, 3486.
30. Fischer, R.; Walther, D.; Gebhardt, P.; Görls, H. Organometallics 2000, 19, 2532.
31. Lee, H.; Hascall, T.; Desrosiers, P. J.; Parkin, G. J. Am. Chem. Soc. 1998, 120, 5830.
32. Cohen, S. A.; Auburn, P. R.; Bercaw, J. E. J. Am. Chem. Soc. 1983, 105, 1136.
33. The labeling scheme used in this paper is adapted from ref 12.
34. Bradley, C. A.; Floras-Torres, S.; Lobkovsky, E.; Abruña, H. D.; Chirik, P. J. Organometallics 2004, 23, 5332.
35. Strazisar, S. A.; Wolczanski, P. T. J. Am. Chem. Soc. 2001, 123, 4728.
36. For examples of β-chloride eliminations in group 4 metallocene chemistry, see: Stockland, R. A.; Foley, S. R.; Jordan, R. F. J. Am. Chem. Soc. 2003, 125, 796.
37. Schaller, C. P.; Cummins, C. C.; Wolczanski, P. T. J. Am. Chem. Soc. 1996, 118, 591.
38. Howard, W. A.; Waters, M.; Parkin, G. J. Am. Chem. Soc. 1993, 115, 4917.
39. For synthesis of similar compounds in cyclopentadienyl-based chemistry, see: Buchwald, S. L.; Nielsen, R. B.; Dewan, J. C. Organometallics 1998, 7, 2324.
40. Bradley, C. A.; Lobkovsky, E.; Keresztes, I.; Chirik, P. J. J. Am. Chem. Soc. 2006, 128, 6454.
41. (a) Brown, H. C.; Lynch, G. J. J. Org. Chem. 1981, 46, 531.
42. (b) Newcomb, M.; Filipkowski, M. A.; Johnson, C. C. Tetrahedron Lett. 1995, 36, 3643.
43. Chirik, P. J.; Day, M. W.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 1999, 121, 10308.
44. Mashima, K.; Yamakawa, M.; Takaya, H. J. Chem. Soc., Dalton Trans. 1991, 2851.
45. Parr, R. G.; Yang, W. Density Functional Theory of Atoms and Molecules; Oxford University Press: New York, 1989.
46. All ΔG values were calculated at 298.15 K.
47. (a) Wiberg, K. B. Tetrahedron 1968, 24, 1083.
48. (b) Wiberg indices are electronic parameters related to the electron density in between atoms. They can be obtained from a Natural Population Analysis and provide an indication of the bond strength.
49. All energies are relative to the initial reactant, A.
50. General considerations and additional experimental procedures are reported in the Supporting Information.