Theoretical study of the oxidative addition of 16-electron d4 [n]-metallocenophane complexes with methane

Journal of Physical Chemistry A

Volumn 105, Issue 14, 2001, Pages 3591-3597

  Su, Ming Der ^a   Chu, San Yan ^b  

^a NATIONAL TSING HUA UNIVERSITY   (Taiwan)

^b KAOHSIUNG MEDICAL UNIVERSITY   (Taiwan)

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL BONDS; COMPLEXATION; METHANE; OXIDATION; TRANSITION METALS;

ENERGY BARRIERS;

ADDITION REACTIONS;

EID: 0035849239     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp003037e     Document Type: Article

References (90)

1. Janowicz, A. H.; Bergman, R. G. J. Am. Chem. Soc. 1982, 104, 352.
2. (b) Janowicz, A. H.; Bergman, R. G. J. Am. Chem. Soc. 1983, 105, 3929.
3. For reviews, see: (a) Parshall, G. W. Acc. Chem. Res. 1975, 8, 113.
4. (b) Bergman, R. G. Science 1984, 223, 902.
5. (c) Janowicz, A. H.; Perima, R. A.; Buchanan, J. M.; Kovac, C. A.; Struker, J. M.; Wax, M. J.; Bergman, R. G. Pure Appl. Chem. 1984, 56, 13.
6. (d) Hill, C. L. Activation and Functionalization of Alkanes; Wiley: New Tork, 1989.
7. (e) Halpern, J. Inorg. Chim. Acta 1985, 100, 41.
8. (f) Ephritikhine, M. New J. Chem. 1986, 10, 9.
9. (g) Jones, W. D.; Feher, F. J. Acc. Chem. Res. 1989, 22, 91.
10. (h) Ryabov, A. D. Chem. Rev. 1990, 90, 403.
11. (i) Davies, J. A.; Watson, P. L.; Liebman, J. F.; Greenberg, A. Selective Hydrocarbon Activation, Principles and Progress; VCH Publishers, Inc.: New York, 1990.
12. (j) Bergman, R. G. J. Organomet. Chem. 1990, 400, 273.
13. (k) Koga, N.; Morokuma, K. Chem. Rev. 1991, 91, 823.
14. (l) Ziegler, T. Chem. Rev. 1991, 91, 651.
15. (m) Bergman, R. G. Adv. Chem. Series 1992, 230, 211.
16. (n) Wasserman, E. P.; Moore, C. B.; Bergman, R. G. Science 1992, 255, 315.
17. (o) Crabtree, R. H. Angew. Chem., Int. Ed. Engl. 1993, 32, 789.
18. (p) Schroder, D.; Schwarz, H. Angew. Chem., Int. Ed. Engl. 1995, 34, 1937.
19. (q) Lees, A. J.; Purwoko, A. A. Coord. Chem. Rev. 1994, 132, 155.
20. (r) Amdtsen, B. A.; Bergman, R. G.; Mobley, T. A.; Peterson, T. H. Acc. Chem. Res. 1995, 28, 154.
21. (s) Ziegler, T. Can. J. Chem. 1995, 73, 743.
22. (t) Arndtsen, B. A.; Bergman, R. G. Science 1995, 270, 1970.
23. (u) Lohrenz, J. C.; Jacobsen, H. Angew. Chem., Int. Ed. Engl. 1996, 35, 1305.
24. (a) Niu, S.; Hall, M. B. Chem. Rev. 2000, 100, 353.
25. (b) Siegbahn, P. E. M.; Blomberg, R. A. Chem. Rev. 2000, 100, 421.
26. Saillard, J. Y.; Hoffmann, R. J. Am. Chem. Soc. 1984, 106, 2006.
27. Dedieu, A. Chem. Rev. 2000, 100, 543.
28. (a) Torrent, M.; Sola, M.; Frenking, G. Chem. Rev. 2000, 100, 439.
29. (b) Frenking, G.; Frohlich, N. Chem. Rev. 2000, 100, 717.
30. (a) Loew, G. H.; Harris, D. L. Chem. Rev. 2000, 100, 407.
31. (b) Alonso, J. A. Chem. Rev. 2000, 100, 637.
32. (c) Harrison, J. F. Chem. Rev. 2000, 100, 679.
33. Green, J. C. Chem. Soc. Rev. 1998, 27, 263.
34. The term ansa (meaning bent handle, attached at both hands) was first introduced with respect to metallocene chemistry by Brintzinger. See: Smith, J. A.; von Seyerl, J.; Huttner, G.; Brintzinger, H. H. J. Organomet. Chem. 1979, 173, 175.
35. For recent reviews, see: (a) Nguyen, P.; Gomez-Elipe, P.; Manners, I. Chem. Rev. 1999, 99, 1515.
36. (b) Hoveyda, A. H.; Morken, J. P. Angew. Chem., Int. Ed. Engl. 1996, 35, 1262.
37. Green, M. L. H.; O'Hare, D. Pure Appl. Chem. 1985, 57, 47 and references therein.
38. (a) Labella, L.; Chernega, A.; Green. M. L. H. J. Chem. Soc., Dalton Trans. 1995, 395.
39. (b) Labella, L.; Chernega, A.; Green. M. L. H. J. Organomet. Chem. 1995, 485, C18-C21.
40. (a) Grebenik, M.; Downs, A. J.; Green, M. L. H.; Perutz, R. N. J. Chem. Soc., Chem. Commun. 1979, 742.
41. (b) Chetwynd-Talbot, J.; Grebnik, P.; Perutz, R. N. Inorg. Chem. 1982, 27, 3647.
42. (c) Cox, P. A.; Grebenik, P.; Perutz, R. N.; Robinson, M. D.; Grinter, R.; Stern, D. R. Inorg. Chem. 1983, 22, 3614.
43. (a) Gianotti, C.; Green, M. L. H. J. Chem. Soc., Chem. Commun. 1972, 1114.
44. (b) Cooper, N. J.; Green, M. L. H.; Mahtab, R. J. Chem. Soc., Dalton Trans. 1979, 1557.
45. (c) Berry, M.; Elmitt, K.; Green, M. L. H. J. Chem. Soc., Dalton Trans. 1979, 1950.
46. (d) Berry, M.; Cooper, N. J.; Green, M. L. H.; Simpson, S. J. J. Chem. Soc., Dalton Trans. 1980, 29.
47. (e) Canestrari, M.; Green, M. L. H. Polyhedron 1982, 7, 629.
48. (f) Green, M. L. H. Pure Appl. Chem. 1984, 56, 47.
49. Green, J.; Jardine, C. N. J. Chem. Soc., Dalton Trans. 1998, 1057.
50. (a) Conway, S. L. J.; Dijkstra, T.; Doerrer, L. H.; Green, J. C.; Green, M. L. H.; Stephens, A. H. H. J. Chem. Soc., Dalton Trans. 1998, 2689.
51. (b) Cherenga, A.; Cook, J.; Green, M. L. H.; Labella, L.; Simpson, S. J.; Souter, J.; Stephens, A. H. H. J. Chem. Soc., Dalton Trans. 1997, 3225.
52. Albright, T. A.; Burdett, J. K.; Whangbo, M. H. Orbital Interaction in Chemistry; Wiley: New York, 1985; p 394.
53. 2}(Me)H]. For more details, see ref 15.
54. (b) It has been demonstrated in ref 15 that the relative singlet-triplet energies in the two species are crucial in determining their relative stabilities.
55. (a) Green, J. C.; Jardine, C. N. J. Chem. Soc., Dalton Trans. 1999, 3767.
56. (b) Green, J. C.; Scottow, A. New J. Chem. 1999, 23, 651.
57. Lauher, J. W.; Hoffmann, R. J. Am. Chem. Soc. 1976, 98, 1729.
58. Ziegler, T.; Cheng, W.; Baerends, E. J.; Ravenek, W. Inorg. Chem. 1988, 27, 3458.
59. (a) McGlynn, S. P.; Azumi, T.; Kinoshita, M. The Triplet State; Prentice-Hall: New York, 1969; pp 190-198.
60. (b) El-Sayed. M. A. J. Phys. Chem. 1963, 38, 2834.
61. (c) El-Sayed, M. A. Acc. Chem. Res. 1968, 1, 8.
62. (a) Su, M.-D. Chem. Phys. Lett. 1995, 237, 317.
63. (b) Su, M.-D. J. Org. Chem. 1995, 60, 6621.
64. (c) Su, M.-D. J. Phys. Chem. 1996, 100, 4339.
65. (d) Su, M.-D. Chem. Phys. 1996, 205, 277.
66. (e) Su, M.-D. J. Org. Chem. 1996, 61, 3080.
67. Suppose the formation of the σ-complex is at the triplet state; this means that it contains 18-electron at the triplet state. Therefore, one electron must go to the antibonding d orbital, which makes the σ-complex itself unstable and then easily get apart. Moreover, as far as we know the calculations about the σ-complex in ref 15, they did not fully optimized the triplet σ-complex, which made their statement doubtful. Indeed, we tried every possibility to fully optimized the triplet σ-complex using different theoretical methods but always failed. Therefore, we had calculated the single-point calculation for the triplet σ-complex using its singlet geometry, and we found that its energy is quite high (about 54 kcal/mol at the B3LYP/
68. LANL2DZ level) compared to the singlet σ-complex. For these reasons, we believe that the oxidative addition reactions proceed on the singlet surface before the triplet σ-complex is formed. Consequently, it is reasonable to focus on the singlet surface.
69. Su, M.-D.; Chu, S.-Y. J. Am. Chem. Soc. 1997, 119, 5373.
70. (a) Su, M.-D.; Chu, S.-Y. Chem. Phys. Lett. 1998, 282, 25.
71. (b) Su, M.-D.; Chu, S.-Y. Organometallics 1997, 16, 1621.
72. (c) Su, M.-D.; Chu, S.-Y. J. Phys. Chem. 1997, 101, 6798.
73. (d) Su, M.-D.; Chu, S.-Y. Eur. J. Chem. 1999, 5, 198.
74. Su, M.-D.; Chu, S.-Y. J. Phys. Chem. 1998, 102, 10159.
75. Su, M.-D.; Chu, S.-Y. Inorg. Chem. 1998, 37, 3400 and references therein.
76. Bullock, R. M.; Headford, C. E. L.; Hennessy, K. M.; Kegley, S. E.; Norton, J. R. J. Am. Chem. Soc. 1989, 111, 3897.
77. Parkin, G.; Bercaw, J. E. Organometallics 1989, 8, 1172.
78. (a) Shaik, S. J. Am. Chem. Soc. 1981, 103, 3691.
79. (b) Shaik, S.; Schlegel, H. B.; Wolfe, S. Theoretical Aspects of Physical Organic Chemistry; John Wiley & Sons Inc.: New York, 1992.
80. (c) Pross, A. Theoretical and Physical Principles of Organic Reactivity; John Wiley & Sons Inc. New York, 1995.
81. Su, M.-D. Inorg. Chem. 1995, 34, 3829.
82. Moore, C. E. Atomic Energy Levels; NBS: Washington, DC, 1971; Vol. III.
83. (a) Becke, A. D. Phys. Rev. A 1988, 38, 3098.
84. (b) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.
85. (c) Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
86. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T.; Petersson, G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Cioslowski, J.; Stefanov, B. B.; Nanayakkara, A.; Challacombe, M.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J. L.; Replogle, E. S.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.; Defrees, D. J.; Baker, J.; Stewart, J. P.; Head-Gordon, M.; Gonzalez, C.; Pople, J. A. Gaussian 94; Gaussian, Inc.: Pittsburgh, PA, 1995.
87. Hay, J. P.; Wadt, W. R. J. Chem. Phys. 1985, 82, 299.
88. Hay, J. P.; Wadt, W. R. J. Chem. Phys. 1985, 82, 284.
89. Dunning, T. H.; Hay, P. J. In Modern Theoretical Chemistry; Schaefer, H. F., Ed., Plenum: New York, 1976; pp 1-28.
90. It has to be emphasized that calculated DFT barrier heights are often, if anything, too low; see: Chemical Applications of Density Functional Theory; Laird, A., Ross, R. B., Ziegler, T., Eds.; American Chemical Society: Washington, DC, 1996. Thus, those barrier numbers might be underestimated by down to several kilocalories per mole. It is believed that using the more sphosticipated theory with larger basis sets should be essential. Nevertheless, the energies obtained at the B3LYP/ LANL2DZ level can, at least, provide the reliably qualitative conclusions.