C-F bond activation by the 14-electron M(X)(PH3)2 (M = Rh, Ir; X = CH3, H, Cl) complex. A density functional study

Journal of the American Chemical Society

Volumn 119, Issue 42, 1997, Pages 10178-10185

  Su, Ming Der ^a   Chu, San Yan ^a  

^a NATIONAL TSING HUA UNIVERSITY   (Taiwan)

Author keywords

[No Author keywords available]

Indexed keywords

HALOGENATED HYDROCARBON;

ARTICLE; CHEMICAL BOND; CHEMICAL REACTION; CHEMICAL STRUCTURE; DENSITY; ENERGY; OXIDATION; REACTION ANALYSIS;

EID: 0030723410     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja971269u     Document Type: Article

References (58)

1. Cobourn, J. W.; Winters, H. R J. Vac. Sci. Technol. 1979, 16, 391.
2. (a) Gottscho, R. A.; Smolinsky, G.; Burton, R. H. J. Appl. Phys. 1982, 53, 5908.
3. (b) Smolinsky, G.; Gottscho, R. A.; Abys, S. A. Ibid. 1983, 54, 3582.
4. (a) Senkan, S. M. Chem. Eng. Prog. 1987, 12, 58.
5. (b) Senkan, S. M. Environ. Sci. Technol. 1988, 22, 368.
6. (c) Rodriquez, C. F.; Bohme, D. K.; Hopkinson, A. C. J. Phys. Chem. 1996, 100, 2942.
7. (d) Papasavva, S.; Illinger, K. H.; Kenny, J. E. J. Phys. Chem. 1996, 100, 10100.
8. (a) Crutzen, P. J. Angew. Chem., Int. Ed Engl. 1996, 35, 1758.
9. (b) Molina, M. J. Ibid. 1996, 35, 1778.
10. Rowland, F. S. Ibid. 1996, 35, 1787.
11. -1. See ref 4.
12. Saunders, G. C. Angew. Chem., Int. Ed. Engl 1996, 35, 2615.
13. Burdeniuc. J.; Jedlicka. B.; Crabtree, R. H. Chem. Ber. 1997, 130, 145 and references therein.
14. (a) Milstein, D.; Calabrese, J. C.; Williams, I. D. J. Am. Chem. Soc. 1986, 108, 6387.
15. (b) Zlota, A. A.; Frolow, F.; Milstein, D. J. Chem. Soc., Chem. Commun. 1989, 1826.
16. It was concluded that the fluoride affinity of highly electrophilic early transition metals tends to preclude their use in catalysis. Similarly, the alkali and alkaline earth metals are not suitable as C-F activation catalysts due to their propensity to form ionic salts with fluoride. Consequently, Richmond et al. suggested that further developments should be sought employing lowvalent electron-rich transition metals. See: Kiplinger, J. L.; Richmond, T. G.; Osterberg, C. E. Chem. Rev. 1994, 94, 373 and references therein.
17. Crabtree, R. H. In Activation and F nationalization of Alkanes', Davies, J. A., Ed., VCH: New York, 1990; p 69.
18. 3 complexes, see: (a) Koga, N.; Morokuma, K. J. Phys. Chem. 1990. 94, 5454. (b) Koga, N.; Morokuma, K. J. Am. Chem. Soc. 1993, 115, 6883- (c) Cundari, T. R. J. Am. Chem. Soc. 1994, 116, 340. (d) Margl, P.; Ziegler, T.; Blochl, P. E. J. Am. Chem. Soc. 1995, 117, 12625.
19. 3 complexes, see: (a) Koga, N.; Morokuma, K. J. Phys. Chem. 1990. 94, 5454. (b) Koga, N.; Morokuma, K. J. Am. Chem. Soc. 1993, 115, 6883- (c) Cundari, T. R. J. Am. Chem. Soc. 1994, 116, 340. (d) Margl, P.; Ziegler, T.; Blochl, P. E. J. Am. Chem. Soc. 1995, 117, 12625.
20. 3 complexes, see: (a) Koga, N.; Morokuma, K. J. Phys. Chem. 1990. 94, 5454. (b) Koga, N.; Morokuma, K. J. Am. Chem. Soc. 1993, 115, 6883- (c) Cundari, T. R. J. Am. Chem. Soc. 1994, 116, 340. (d) Margl, P.; Ziegler, T.; Blochl, P. E. J. Am. Chem. Soc. 1995, 117, 12625.
21. 3 complexes, see: (a) Koga, N.; Morokuma, K. J. Phys. Chem. 1990. 94, 5454. (b) Koga, N.; Morokuma, K. J. Am. Chem. Soc. 1993, 115, 6883- (c) Cundari, T. R. J. Am. Chem. Soc. 1994, 116, 340. (d) Margl, P.; Ziegler, T.; Blochl, P. E. J. Am. Chem. Soc. 1995, 117, 12625.
22. Botor, J. P.: Edwards, J. G. J. Chem. Phys. 1984, 81, 2185.
23. Crepin, C.; Verges, J.; Amiot, C. Chem. Phys. Lett. 1984, 122, 10-
24. Albright, T. A.; Burden, J. K.; Whangbo, M. H. Orbital Interaction in Chemistry; Wiley: New York, 1985; p 339.
25. i, which could be labeled wrong, based on MP4SDTQ results (see ref 1 la).
26. (a) Su, M.-D. Chem. Phys. Lett. 1995, 237, 317.
27. (b) Su, M.-D. J. Org. Chem. 1995, 60, 6621.
28. (c) Su, M.-D. J. Phys. Chem. 1996, 100, 4339.
29. (d) Su, M.-D. Chem. Phys. 1996, 205, 277.
30. (e) Su, M.-D. J. Org. Chem. 1996, 61, 3080.
31. Burden, J. K.; Albright, T. A. Inorg. Chem. 1979, 18, 2112.
32. (a) For 16-electron CpML systems, see: Su, M.-D.; Chu, S.-Y. Organometallics 1997, 16, 1621.
33. (b) For 14-electron ML, systems, see: Su, M.-D.; Chu, S.-Y. Submitted.
34. To our knowledge, it was experimentally found that stable oxidative addition products with alkanes will be found predominantly in the third row; e.g., for oxidative addition of indium and rhodium intermediates to alkane C-H bonds, the products formed in the latter case are much less stable and undergo reductive elimination at -20 °C. For details, see: Bergman, R. G. Science 1984, 223, 902.
35. Calculated DFT barrier heights are often, if anything, too low; see Chemical Applications of Density Functional Theory; Laird, A., Ross, R. B., Zeigler, T., Eds.; American Chemical Society: Washington, DC, 1996. We would like to thank referee B for bringing this reference to our attention.
36. Su, M.-D. Inorg. Chem. 1995, 34, 3829.
37. (a) Su, M.-D.; Chu, S.-Y. J. Am. Chem. Soc. 1997, 119, 5373.
38. (b) Su, M.-D.; Chu, S.-Y. J. Phys. Chem. in press.
39. (a) Shaik, S.; Schlegel, H. B.; Wolfe, S. Theoretical Aspects of Physical Organic Chemistry; John Wiley & Sons Inc.: New York, 1992.
40. (b) Press, A. Theoretical and Physical Principles of Organic Reactivity; John Wiley & Sons Inc.: New York. 1995.
41. 2:, it is in principle conceivable that, using the "isolobal analogy" (see: Hoffmann, R. Angew. Chem., Int. Ed. Engl. 1982, 21, 711), the same predictions could also be applied to organometallic systems.
42. 3[CF] contribute very little, if at all, to the total wavefunction W. See ref 21.
43. Siegbahn, P. E. M. J. Am. Chem. Soc. 1996, 118, 1487.
44. (a) Becke, A. D. Phys. Rev. A 1988, 38, 3098.
45. (b) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.
46. (c) Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
47. Ricca, A.; Bauschlicher, C. W. Theor. Chim. Acta. 1995, 92, 123.
48. Hay, J. P.; Wadt, W. R. J. Chem. Phys. 1985, 52, 299.
49. Hay, J. P.; Wadt, W. R. J. Chem. Phys. 1985, 82, 284.
50. Gaussian 94, Revision B.2: M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. Keith, G. A. Peterson, J. A. Montgomery, K. Raghavachari, M. A. AI-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, J. Cioslowski, B. B. Stefanov, A. Nanayakara, M. Challacombe, C. Y. Peng, P. Y. Ayala, W. Chen, M. W. Wong, J. L. Andres, E. S. Replogle, R. Gomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzalez, and J. A. Pople, Gaussian, Inc., Pittsburgh PA, 1995.
51. Dunning, T. H.; Hay, P. J. Modern Theoretical Chemistry; Schaefer, H. F., Ed.; Plenum: New York, 1976; pp 1-28.
52. (a) Musaev, D. G.; Morokuma, K. J. Phys. Chem. 1996, 100, 6509.
53. (b) Cui, Q.; Musaev, D. G.; Morokuma, K. Organometallics, 1997, 16, 1355.
54. (a) Dunning, T. H., Jr. J. Chem. Phys. 1970, 53, 2823.
55. (b) Dunning, T. H., Jr.; Hay, P. J. Methods of Electronic Structure Theory; Schaefer, H. F., III, Ed.; Plenum Press: New York, 1977; Vol. 2.
56. (a) For C and F, see ref 34.
57. (b) For P and Cl, see: Magnusson, E.; Schaefer, H. F., III J. Chem. Phys. 1985,-83, 5721.
58. Ehlers, A. W.; Bohme, M.; Dapprich, S.; Gobbi, A.; Hollwarth, A.; Jonas, V.; Kohler, K. F.; Stegmann, R.; Veldkamp, A.; Frenking, G. Chem. Phys. Lett., 1993, 208, 111.