C-H bond activation in aqueous solution: Kinetics and mechanism of H/D exchange in alcohols catalyzed by molybdocenes

Journal of the American Chemical Society

Volumn 122, Issue 39, 2000, Pages 9427-9434

  Balzarek, Christoph ^a   Weakley, Timothy J R ^a   Tyler, David R ^a  

^a UNIVERSITY OF OREGON   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CARBENE; CARBON; HYDROGEN; KETONE; LIGAND; METAL COMPLEX; MOLYBDENUM COMPLEX; MOLYBDOCENE; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; CATALYST; CHEMICAL BINDING; CHEMICAL REACTION KINETICS; CHEMICAL STRUCTURE; COMPLEX FORMATION; CRYSTALLOGRAPHY; DISSOCIATION; HYDROGEN BOND; ION EXCHANGE; REACTION ANALYSIS; SYNTHESIS;

EID: 0034605460     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja001535v     Document Type: Article

References (67)

1. Toney, J. H.; Marks, T. J. J. Am. Chem. Soc. 1985, 107, 947-953.
2. Mokdsi, G.; Harding, M. M. J. Organomet. Chem. 1998, 565, 29-35.
3. Murray, J. H.; Harding, M. M. J. Med. Chem. 1994, 37, 1936-1941.
4. Harding, M. M.; Prodigalidad, M.; Lynch, M. J. J. Med. Chem. 1996, 39, 5012-5016.
5. Spreer, L. O.; Shah, I. Inorg. Chem. 1981, 20, 4025-4027.
6. Kuo, L. Y.; Kanatzidis, M. G.; Marks, T. J. J. Am. Chem. Soc. 1987, 109, 7207-7209.
7. Kuo, L. Y.; Kanatzidis, M. G.; Sabat, M.; Tipton, A. L.; Marks, T. J. J. Am. Chem. Soc. 1991, 113, 9027-9045.
8. Kuo, L. Y.; Kuhn, S.; Ly, D. Inorg. Chem. 1995, 34, 5341-5345.
9. Kuo, L. Y.; Barnes, L. A. Inorg. Chem. 1999, 38, 814-817.
10. Avey, A.; Tenhaeff, S. C.; Weakley, T. J. R.; Tyler, D. R. Organometallics 1991, 10, 3607-3613.
11. Avey, A.; Tyler, D. R. Organometallics 1992, 11, 3856-3863.
12. Tyler, D. R. Organometallic Radical Chemistry in Aqueous Solution. In Aqueous Organometallic Chemistry and Catalysis; Kluwer Academic Publishers: Dordrecht, 1995; pp 47-60.
13. Baxley, G. T.; Miller, W. K.; Lyon, D. K.; Miller, B. E.; Nieckarz, G. F.; Weakley, T. J. R.; Tyler, D. R. Inorg. Chem. 1996, 35, 6688-6693.
14. Nieckarz, G. F.; Weakley, T. J. R.; Miller, W. K.; Miller, B. E.; Lyon, D. K.; Tyler, D. R. Inorg. Chem. 1996, 35, 1721-1724.
15. Baxley, G. T.; Weakley, T. J. R.; Miller, W. K.; Lyon, D. K.; Tyler, D. R. J. Mol. Catal. A: Chem. 1997, 116, 191-198.
16. Yoon, M.; Tyler, D. R. Chem. Commun. 1997, 639-640.
17. For reviews see: (a) Horváth, I.; Joó, F. Aqueous Organometallic Chemistry and Catalysis; Kluwer Academic Press: Dordrecht, 1995. (b) Cornils, B.; Herrmann, W. A. Aqueous Phase Organometallic Catalysis; Wiley-VCH: Weinheim, 1998. (c) Herrmann, W. A.; Kohlpaintner, C. W. Angew. Chem. 1993, 32, 1524-1544.
18. For reviews see: (a) Horváth, I.; Joó, F. Aqueous Organometallic Chemistry and Catalysis; Kluwer Academic Press: Dordrecht, 1995. (b) Cornils, B.; Herrmann, W. A. Aqueous Phase Organometallic Catalysis; Wiley-VCH: Weinheim, 1998. (c) Herrmann, W. A.; Kohlpaintner, C. W. Angew. Chem. 1993, 32, 1524-1544.
19. For reviews see: (a) Horváth, I.; Joó, F. Aqueous Organometallic Chemistry and Catalysis; Kluwer Academic Press: Dordrecht, 1995. (b) Cornils, B.; Herrmann, W. A. Aqueous Phase Organometallic Catalysis; Wiley-VCH: Weinheim, 1998. (c) Herrmann, W. A.; Kohlpaintner, C. W. Angew. Chem. 1993, 32, 1524-1544.
20. Balzarek, C.; Weakley, T. J. R.; Kuo, L. Y.; Tyler, D. R. Organometallics 2000, 19, 2927-2931.
21. Balzarek, C.; Tyler, D. R. Angew. Chem., Int. Ed. 1999, 38, 2406-2408.
22. Parkin, G.; Bercaw, J. E. Organometallics 1989, 8, 1172-1179.
23. Arndtsen, B. A.; Bergman, R. G.; Mobley, T. A.; Peterson, T. H. Acc. Chem. Res. 1995, 28, 154-162.
24. Shilov, A. E.; Shul'pin, G. B. Chem. Rev. 1997, 97, 2879-2932.
25. Regen, S. L. J. Org. Chem. 1974, 39, 260-261.
26. Stahl, S. S.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 1996, 118, 5961-5976.
27. Green, M. L. H.; Lindsell, W. E. J. Chem. Soc. A 1967, 1455-1458.
28. Ribeiro da Silva, M. A. V.; Ribeiro da Silva, M. M. C.; Dias, A. R. J. Organomet. Chem. 1988, 345, 105-115.
29. Hunger, M.; Limberg, C.; Kircher, P. Angew. Chem., Int. Ed. 1999, 38, 1105-1108.
30. Carmichael, A. J.; McCamley, A. J. Chem. Soc., Dalton Trans. 1997, 93-98.
31. 2 was determined by neutron diffraction as 1.685(3) Å: (a) Schultz, A. J.; Stearley, K. L.; Williams, J. M.; Mink, R.; Stucky, G. D. Inorg. Chem. 1977, 16, 3303-3306. Other Mo-H bond length were found to be of the order of 1.7 Å: (b) Azevedo, C. G.; Calhorda, M. J.; Carrondo, M. A. A. F. d. C. T.; Dias, A. R.; Felix, V.; Romao, C. C. J. Organomet. Chem. 1990, 391, 345-360. (c) Koloski, T. S.; Pestana, D. C.; Carroll, P. J.; Berry, D. H. Organometallics 1994, 13, 489-499.
32. 2 was determined by neutron diffraction as 1.685(3) Å: (a) Schultz, A. J.; Stearley, K. L.; Williams, J. M.; Mink, R.; Stucky, G. D. Inorg. Chem. 1977, 16, 3303-3306. Other Mo-H bond length were found to be of the order of 1.7 Å: (b) Azevedo, C. G.; Calhorda, M. J.; Carrondo, M. A. A. F. d. C. T.; Dias, A. R.; Felix, V.; Romao, C. C. J. Organomet. Chem. 1990, 391, 345-360. (c) Koloski, T. S.; Pestana, D. C.; Carroll, P. J.; Berry, D. H. Organometallics 1994, 13, 489-499.
33. 2 was determined by neutron diffraction as 1.685(3) Å: (a) Schultz, A. J.; Stearley, K. L.; Williams, J. M.; Mink, R.; Stucky, G. D. Inorg. Chem. 1977, 16, 3303-3306. Other Mo-H bond length were found to be of the order of 1.7 Å: (b) Azevedo, C. G.; Calhorda, M. J.; Carrondo, M. A. A. F. d. C. T.; Dias, A. R.; Felix, V.; Romao, C. C. J. Organomet. Chem. 1990, 391, 345-360. (c) Koloski, T. S.; Pestana, D. C.; Carroll, P. J.; Berry, D. H. Organometallics 1994, 13, 489-499.
34. Ko, J. J.; Bockman, T. M.; Kochi, J. K. Organometallics 1990, 9, 1833-1842.
35. L. Y. Kuo, personal communication.
36. It is important to note that a σ-bonded ketone complex could be considered as an alternative formulation of the ketone hydride complex 4. Trispyrazolylborate complexes of Mo and W have recently been shown to contain σ- or π-bonded ketones, depending on steric strain: Schuster. D. M.; White, P. S.; Templeton, J. L. Organometallics 2000, 19, 1540-1548.
37. Gambarotti, S.; Floriani, C.; Chiesi-Villa, A.; Guatini, C. J. Am. Chem. Soc. 1985, 107, 2985-2986.
38. Herberich, G. E.; Okuda, J. Angew. Chem., Int. Ed. Engl. 1985, 24, 402.
39. Okuda, J.; Herberich, G. E. Organometallics 1987, 6, 2331-2336.
40. See footnote 28 in ref 35.
41. Saura-Llamas, I.; Gladysz, J. A. J. Am. Chem. Soc. 1992, 114, 2136-2144.
42. Benfield, F. W. S.; Green, M. L. H. J. Chem. Soc., Dalton Trans. 1974, 1324-1331.
43. 2+.
44. Zassinovich, G.; Mestroni, G.; Gladiali, S. Chem. Rev. 1992, 92, 1051-1069.
45. Noyori, R.; Hashigushi, S. Acc. Chem. Res. 1997, 30, 97-102.
46. (a) Aranyos, A.; Csjernyik, G.; Szabó, K.; Bäckvall, J.-E. Chem. Commun. 1999, 351-352.
47. (b) Laxmi, Y. R. S.; Bäckvall, J.-E. Chem. Commun. 2000, 611-612.
48. Under some circumstances (unsatisfactory shimming, line broadening as an effect of temperature beyond resolution of the two individual resonances) and at early reaction times (A resonances much bigger than and therefore overlapping with B), separation of the A and B resonances is not possible. Rate constants can be obtained, however, from evaluation of the integral over the entire methylene region.
49. This assumption does not take into account a secondary kinetic isotope effect arising from the nonexchanging C-D bond.
50. -0.5k1t.
51. Nonlinear data fitting was carried out with the program pro Fit 5.1 using the Levenberg-Marquardt algorithm: QuantumSoft, Postfach 6613, CH-8023, Zürich, Switzerland.
52. 2O solution (it was difficult to adjust the pD to exactly 6.5). Because the H/D reaction slows down with decreasing pH/pD, the calculated primary kinetic isotope effect can be considered a lower limit.
53. 1H NMR spectrum in the Cp′ region of 1 and 2 changes significantly, indicating that structural changes occur. These changes in the structure of the active catalyst may also contribute to the decrease in rate.
54. D determination without pH correction, see: Jensen, C. M.; Trogler, W. C. J. Am. Chem. Soc. 1986, 108, 723-729.
55. Li, M.-Y.; San Filippo, J., Jr. Organometallics 1983, 2, 554-555.
56. Whitesides, G. M.; Gaasch, J. F.; Stedronsky, E. R. J. Am. Chem. Soc. 1972, 94, 5258-5270, ref 36.
57. Activation entropies of similar magnitude have been observed previously in reactions with β-hydrogen-elimination-type rate-determining steps: (a) Van der Boom, M. E.; Higgitt, C. L.; Milstein, D. Organometallics 1999, 18, 2413-2419 and references therein. (b) Hoffman, D. M.; Lappas, D.; Wierda, D. A. Organometallics 1997, 16, 972-978. (c) Blum, O.; Milstein, D. J. Organomet. Chem 2000, 593-594, 479-484.
58. Activation entropies of similar magnitude have been observed previously in reactions with β-hydrogen-elimination-type rate-determining steps: (a) Van der Boom, M. E.; Higgitt, C. L.; Milstein, D. Organometallics 1999, 18, 2413-2419 and references therein. (b) Hoffman, D. M.; Lappas, D.; Wierda, D. A. Organometallics 1997, 16, 972-978. (c) Blum, O.; Milstein, D. J. Organomet. Chem 2000, 593-594, 479-484.
59. Activation entropies of similar magnitude have been observed previously in reactions with β-hydrogen-elimination-type rate-determining steps: (a) Van der Boom, M. E.; Higgitt, C. L.; Milstein, D. Organometallics 1999, 18, 2413-2419 and references therein. (b) Hoffman, D. M.; Lappas, D.; Wierda, D. A. Organometallics 1997, 16, 972-978. (c) Blum, O.; Milstein, D. J. Organomet. Chem 2000, 593-594, 479-484.
60. Lowry, T. H.; Richardson, K. S. Mechanism and Theory in Organic Chemistry, 3rd ed.; Harper Collins Publishers: New York, 1987.
61. Perrin, D. D.; Armarego, W. L. F. Purification of Laboratory Chemicals, 3rd ed., Pergamon Press: Oxford, 1988.
62. Luo, L.; Lanza, G.; Fragala, I. L.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1998, 120, 3111-3122.
63. Glasoe, P. K.; Long, F. A. J. Phys. Chem. 1960, 64, 188-190.
64. Mikkelsen, K.; Nielsen, S. O. J. Phys. Chem. 1960, 64, 632-637.
65. Altomare, A.; Cascarano, G.; Giacovazzo, C.; Guigliardi, A.; Burla, M. C.; Polidori, G.; Camalli, N. J. Appl. Crystallogr. 1994, 27, 435.
66. Walker, N.; Stuart, D. Acta Crystallogr., A 1983, 39, 158-166.
67. Molecular Structures Corporation, 3200A Research Forest Drive, The Woodlands, TX 77381. teXsan Software for Single-Crystal Structure Analysis, version 1.7, 1997.