Physical organic chemistry of transition metal carbene complexes. 18. Kinetics of reversible cyclization of the Fischer carbene complexes (CO)5M=C(SCH2CH2OH)Ph and (CO)5M=C(OCH2CH2OH)Ph (M = Cr, W) in aqueous acetonitrile

Journal of the American Chemical Society

Volumn 122, Issue 7, 2000, Pages 1352-1359

  Bernasconi, Claude F ^a   Ali, Mahammad ^a,b   Lu, Felice ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

^b VIDYASAGAR COLLEGE   (India)

Author keywords

[No Author keywords available]

Indexed keywords

ACETONITRILE; CARBENE; CHROMIUM DERIVATIVE; METAL COMPLEX; TUNGSTEN DERIVATIVE;

ARTICLE; CHEMICAL REACTION KINETICS; CYCLIZATION; EQUILIBRIUM CONSTANT; ORGANIC CHEMISTRY; PHYSICAL CHEMISTRY; REACTION ANALYSIS;

EID: 0033996380     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja993418+     Document Type: Article

References (50)

1. Part 17: Bernasconi, C. F.; Ali, M. J. Am. Chem. Soc. 1999, 121, 11384.
2. -, etc.
3. Bernasconi, C. F.; Kittredge, K. W.; Flores, F. X. J. Am. Chem. Soc. 1999, 121, 6630.
4. -]).
5. 6
6. Bernasconi, C. F.; Sun, W. J. Am. Chem. Soc. 1993, 115, 12526.
7. -1 for 8-CrOOH (Table 1).
8. Bernasconi, C. F.; Flores, F. X.; Kittredge, K. W. J. Am. Chem. Soc. 1997, 119, 2103.
9. 3
10. (a) Jencks, W. P. Acc. Chem. Res. 1976, 9, 425.
11. (b) Jencks, W. P. Acc. Chem. Res. 1980, 13, 161.
12. (c) Jencks, W. P. Chem. Soc. Res. 1981, 10, 345.
13. 12
14. Hansch, C.; Leo, A.; Taft, R. W. Chem. Rev. 1991, 91, 165.
15. 14 and water (15.74) in water.
16. Ballinger, P.; Long, F. A. J. Am. Chem. Soc. 1960, 82, 795.
17. (a) Kirby, A. J. The Anomeric Effect and Related Stereoelectronic Effects of Oxygen; Springer-Verlag: Berlin, 1983.
18. (b) Schleyer, P. v. R.; Jemmis, E. D.; Spitznagel, G. W. J. Am. Chem. Soc. 1985, 107, 6393.
19. (a) Hine, J.; Klueppl, A. W. J. Am. Chem. Soc. 1974, 96, 2924.
20. (b) Wiberg, K. B.; Squires, R. R. J. Chem. Thermodyn. 1979, 11, 773.
21. (c) Harcourt, M. P.; More O'Ferrall, R. A. Bull. Soc. Chim. Fr. 1988, 407.
22. 12
23. 1 = 1.
24. Marcus, R. A. J. Chem. Phys. 1965, 43, 679.
25. 0 values are used for comparative purposes which is our focus.
26. (a) Jencks, D. A.; Jencks, W. P. J. Am. Chem. Soc. 1977, 99, 7948.
27. (b) Jencks, W. P. Chem. Rev. 1985, 85, 511.
28. (a) Bernasconi, C. F. Acc. Chem. Res. 1987, 20, 301.
29. (b) Bernasconi, C. F. Acc. Chem. Res. 1992, 25, 9.
30. (c) Bernasconi, C. F. Adv. Phys. Org. Chem. 1992, 27, 119.
31. Bernasconi, C. F.; Ketner, R. J.; Chen, X.; Rappoport, Z. Can. J. Chem. 1999, 77, 584.
32. 22
33. Bernasconi, C. F.; Flores, F. X.; Gandler, J. R.; Leyes, A. E. Organometallics 1994, 13, 2186.
34. Bernasconi, C. F.; Ketner, R. J.; Chen, X.; Rappoport, Z. J. Am. Chem. Soc. 1998, 120, 7461.
35. (a) Hupe, D. J.; Jencks, W. P. J. Am. Chem. Soc. 1977, 99, 451.
36. (b) Jencks, W. P.; Brant, S. R.; Gandler, J. R.; Fendrich, G.; Nakamura, C. J. Am. Chem. Soc. 1982, 104, 7054.
37. -2 pathway is 14.
38. Bernasconi, C. F.; García-Río, L. To be published.
39. Bernasconi, C. F.; Sun, W. Organometallics 1997, 16, 1926.
40. Pip = piperidine.
41. Bernasconi, C. F.; Ali, M. J. Am. Chem. Soc. 1999, 121, 3039.
42. Numbering in Table 2.
43. (a) Kirby, A. J. Adv. Phys. Org. Chem. 1980, 17, 183.
44. (b) Mandolini, L. Adv. Phys. Org. Chem. 1986, 22, 1.
45. -1- (inter) ratio is obtained by dividing the experimental ratio by 4.58.
46. 2)Ph and 2-M) relative to their respective precursors but also more stable towards decomposition. However, since the nature of the decomposition is not known, not too much significance should be attached to these observations. The fact that there is little difference in the EM values between the Cr and W derivatives but a large difference in the stability toward decomposition, with the cyclic W adducts being more stable, indicates that there is no simple relationship between the two types of stabilities.
47. 1).
48. 34b treatment of this subject which uses a formalism based on thermodynamic relationships leads to the same conclusions.
49. Bemasconi, C. F.; Howard, K. J. Am. Chem. Soc. 1982, 104, 7248.
50. Allen, A. D.; Tidwell, T. T. J. Am. Chem. Soc. 1987, 109, 2774.