Intermolecular C-H activation of hydrocarbons by tungsten alkylidene complexes: An experimental and computational mechanistic study

Organometallics

Volumn 20, Issue 23, 2001, Pages 4939-4955

  Adams, Craig S ^a   Legzdins, Peter ^a   McNeil, W Stephen ^a  

^a UNIVERSITY OF BRITISH COLUMBIA   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

BOND ACTIVATION; THERMOLYSIS; TUNGSTEN ALKYLIDENE COMPLEXES;

ACTIVATION ENERGY; ADDITION REACTIONS; AROMATIC HYDROCARBONS; CHEMICAL ACTIVATION; CHEMICAL BONDS; DERIVATIVES; DISCRETE FOURIER TRANSFORMS; MOLECULAR ORIENTATION; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; PYROLYSIS; SUBSTRATES; TUNGSTEN COMPOUNDS;

ORGANOMETALLICS;

EID: 0035851940     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om010380c     Document Type: Article

References (79)

1. (a) Shilov, A. E.; Shul'pin, G. B. Activation and Catalytic Reactions of Saturated Hydrocarbons in the Presence of Metal Complexes; Kluwer Academic: Dordrecht, The Netherlands, 2000.
2. (b) Arndtsen, B. A.,; Bergman, R. G.; Mobley, T. A.; Peterson, T. H. Acc. Chem. Res. 1995, 28, 154-162.
3. (c) Crabtree, R. H. Chem. Rev. 1995, 95, 987-1007.
4. (d) Stahl, S. S.; Labinger, J. A.; Bercaw, J. E. Angew. Chem., Int. Ed. Engl. 1998, 37, 2180-2192.
5. (a) Peterson, T. H.; Golden, J. T.; Bergman, R. G. J. Am. Chem. Soc. 2001, 123, 455-462 and refs 1-27 and 32-35 therein.
6. Stahl, S. S.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 1996, 118, 5961-5976 and refs 8-21 therein.
7. Slaughter, L. M.; Wolczanski, P. T.; Klinckman, T. R.; Cundari, T. R. J. Am. Chem. Soc. 2000, 122, 7953-7975 and refs 10-17 therein.
8. For an inspiring illustration of this fact, Johnson, J. A.; Sames, D. J. Am. Chem. Soc. 2000, 122, 6321-6322.
9. (a) Tran, E.; Legzdins, P. J. Am. Chem. Soc. 1997, 119, 5071-5072.
10. (b) Adams, C. S.; Legzdins, P.; Tran, E. J. Am. Chem. Soc. 2001, 123, 612-624.
11. For the three other reported examples of intermolecular C-H activations by alkylidene complexes, (a) Coles, M. P.; Gibson, V. C.; Clegg, W.; Elsegood, R. R. J.; Porrelli, P. A. J. Chem. Soc., Chem. Commun. 1996, 1963-1964.
12. (b) van der Heijden, H.; Hessen, B. J. Chem. Soc., Chem. Commun. 1995, 145-146.
13. (c) Cheon, J.; Rogers, D. M.; Girolami, G. S. J. Am. Chem. Soc. 119, 6804-6813.
14. Poli, R.; Smith, K. M. Organometallics 2000, 19, 2858-2867.
15. McDade, C.; Green, J. C.; Bercaw, J. E. Organometallics 1982, 1, 1629-1634.
16. Hall, C.; Perutz, R. N. Chem. Rev. 1996, 96, 3125-3146.
17. (a) Feher, F. J.; Jones, W. D. J. Am. Chem. Soc. 1984, 106, 1650-1663.
18. (b) Jones, W. D.; Feher, F. J. J. Am. Chem. Soc. 1986, 108, 4814-4819.
19. (c) Selmeczy, A. D.; Jones, W. D.; Osman, R.; Perutz, R. N. Organometallics 1995, 14, 5677-5685.
20. (d) Jones, W. D.; Hessel, E. T. J. Am. Chem. Soc. 1992, 114, 6087-6095.
21. (e) Wick, D. D.; Reynolds, K. A.; Jones, W. D. J. Am. Chem. Soc. 1999, 121, 3974-3983.
22. (f) Schaefer, D. F., II; Wolczanski, P. T. J. Am. Chem. Soc. 1998, 120, 4881-4882.
23. (g) Periana, R. A.; Bergman, R. G. J. Am. Chem. Soc. 1986, 108, 7346-7355.
24. (h) Stoutland, P. O.; Bergman, R. G. J. Am. Chem. Soc. 1988, 110, 5732-5744.
25. (i) McGhee, W. D.; Bergman, R. G. J. Am. Chem. Soc. 1988, 110, 4246-4262.
26. (j) Mobley, T. A.; Schade, C.; Bergman, R. G. Organometallics 1998, 17, 3574-3587.
27. (a) Bullock, R. M.; Headford, C. E. L.; Hennessy, K. M.; Kegley, S. E.; Norton, J. E. J. Am. Chem. Soc. 1989, 111, 3897-3908.
28. (b) Parkin, G.; Bercaw, J. E. Organometallics 1989, 8, 1172-1179.
29. (c) Gould, G. L.; Heinekey, D. M. J. Am. Chem. Soc. 1989, 111, 5502-5504.
30. (e) Gross, C. L.; Girolami, G. S. J. Am. Chem. Soc. 1998, 120, 6605-6606.
31. (f) Chernega, A.; Cook, J.; Green, M. L. H.; Labella, L.; Simpson, S. J.; Souter, J.; Stephens, A. H. H. J. Chem. Soc., Dalton Trans. 1997, 3225-3243.
32. 1).
33. The synclinal and anticlinal orientations of the methylene protons are defined with respect to the other M-C bond in the preferred stereochemistry in which both alkyl ligands are pointing away from the Cp* ligand.
34. 0 are likely due to a combination of the assumptions made in the calculations (see Experimental Section) and the uncertainties in the average mass spectral intensities.
35. x are sufficiently unstable toward β-H elimination of a second equivalent of neopentane under these conditions that the analysis of the noepentane isotopomer distribution from this reaction could not be included in Tables 1 and 2. See ref 6b for details.
36. -1 at 91 °C and the value of 2.4 is an underestimation of the true isotope effect for α-H neopentane elimination in this system.
37. Booji, M.; Deelman, B.-J.; Duchateau, R.; Postma, D. S.; Meetsma, A.; Teuben, J. H. Organometallics 1993, 12, 3531-3540.
38. Note that activation now refers to both coordination of the substrate and cleavage of the C-H bonds. For irreversible activations, only the coordinate step need be irreversible for the substrate to be nonlabile once activated.
39. For examples in which C-H bond scission is rate-limiting and the intermolecular KIEs are significantly large, see: (a) Reference 4.
40. (b) Jiang, Q.; Pestana, D. C.; Carroll, P. J.; Berry, D. H. Organometallics 1994, 13, 3679-3691.
41. (c) Watson, P. L. J. Am. Chem. Soc. 1983, 105, 6491-6493.
42. For a good illustration of the differences between these mechanisms, see: Cotton, F. A.; Wilkinson, G.; Gaus, P. L. Basic Inorganic Chemistry, 2nd ed.; Wiley: Toronto, 1987; pp 176-179.
43. 4, do not show any significant solvent effects, which would be expected if the solvent is involved in the displacement of neopentane from the metal's coordination sphere.
44. Schaller, C. P.; Cummins, C. C.; Wolczanski, P. T. J. Am. Chem. Soc. 1996, 118, 591-611.
45. Note that "reversible C-H bond scission" refers only to the C-H bond cleavage event, not to the overall activation process, which represents both substrate coordination and cleavage of a substrate C-H bond.
46. (a) Feher, F. J.; Jones, W. D. J. Am. Chem. Soc. 1984, 106, 1650-1663.
47. (b) Chin, R. M.; Dong, L.; Duckett, S. B.; Partridge, M. G.; Jones, W. D.; Perutz, R. N. J. Am. Chem. Soc. 1993, 115, 7685-7695.
48. (c) Sweet, J. R.; Graham, W. A. G. J. Am. Chem. Soc. 1983, 105, 304-306.
49. (a) Erker, G. J. Organomet. Chem. 1977, 134, 189-202.
50. (b) Debad, J. D.; Legzdins, P.; Lumb, S. A.; Rettig, S. J.; Batchelor, R. J.; Einstein, F. W. B. Organometallics 1999, 18, 3414-3428
51. (c) Price, R. T.; Andersen, R. A.; Muetterities, E. L. J. Organmet. Chem. 1989, 376, 407-417.
52. The corresponding incorporation of H into the phenyl region is obscured by signals for the aryl protons of the benzyl ligand.
53. (a) Legzdins, P.; Jones, R. H.; Phillips, E. C.; Yee, V. C.; Trotter J.; Einstein, F. W. B. Organometallics 1991, 10, 986-1002.
54. (b) Dryden, N. H.; Legzdins, P.; Trotter, J.; Yee, V. C. Organometallics 1991, 10, 2857-2870.
55. 3-C,H)-phenylmethane coordination mode.
56. Bau, R.; Mason, S. A.; Patrick, B. O.; Adams, C. S.; Sharp, W. B.; Legzdins, P. Organometallics, in press.
57. Levine, I. N. Quantum Chemistry, 5th ed.; Prentice Hall: Upper Saddle River, NJ, 2000.
58. The difference may be due in part to the difference between gas-phase and solution-phase free energies, to the inflexible basis set employed, and to the limitations of the B3LYP DFT approach. However, the formations of methylidene analogues of neopentylidene complexes have been found to be energetically less favorable in both theoretical and experimental studies. For example, see: (a) Wu, Y.-D.; Peng, Z. H.; Xue, Z. J. Am. Chem. Soc. 1996, 118, 9772-9777.
59. (b) Warren, T. H.; Schrock, R. R.; Davis, W. M. J. Organomet. Chem. 1998, 569, 125-137.
60. Legzdins, P.; Veltheer, J. E. Acc. Chem. Res. 1993, 26, 41-48.
61. For some examples, see: (a) Schaller, C. P.; Wolczanski, P. T. Inorg. Chem. 1993, 32, 131-144.
62. (b) Thompson, M. E.; Baxter, S. M.; Bulls, R.; Burger, B. J.; Nolan, M. C.; Santarsiero, B. D.; Schaefer, W. P.; Bercaw, J. E. J. Am. Chem. Soc. 1987, 109, 203-219.
63. (c) Wang, C.; Ziller, J. W.; Flood, T. C. J. Am. Chem. Soc. 1995, 117, 1647-1648.
64. Legzdins, P.; Rettig, S. J.; Ross, K. J.; Batchelor, R. J.; Einstein, F. W. B. Organometallics 1995, 14, 5579-5587.
65. Dryden, N. H.; Legzdins, P.; Rettig, S. J.; Veltheer, J. E. Organometallics 1992, 11, 2583-2590.
66. Legzdins, P.; Rettig, S. J.; Veltheer, J. E. Organometallics 1993, 12, 3575-3585.
67. Debad, J. D.; Legzdins, P.; Batchelor, R. J.; Einstein, F. W. B. Organometallics 1993, 12, 2094-2102.
68. 2O, H/D abundances were calculated using 1 D = 1 H.
69. Harris, D. C. Quantitative Chemical Analysis, 2nd ed.; W. H. Freeman; New York, 1987; pp 44-55.
70. Origin 5.0 Microcal Software Inc., 1991-1997.
71. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.,; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; Johnson, B. G.; Chen, W.; Wong, M. W.; Andres, J. L.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98, revision A.9; Gaussian, Inc.: Pittsburgh, PA, 1998.
72. Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5652.
73. (a) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. 1988, B37, 785-789.
74. (b) Volko, S. H.; Wilk, L.; Nusair, N. Can J. Phys. 1980, 58, 1200-1211.
75. Dunning, T. H., Jr.; Hay, P. J. In Modern Theoretical Chemistry; Schaefer, H. F., III, Ed.; Plenum Press: New York, 1976; pp 1-28.
76. (a) Hay, P. J.; Wadt, W. R. J. Chem. Phys. 1985, 82, 270-283.
77. (b) Wadt, W. R.; Hay, P. J. J. Chem. Phys. 1985, 82, 284-298.
78. (c) Hay, P. J.; Wadt, W. R. J. Chem. Phys. 1985, 82, 299-310.
79. Schaftenaar, G.; Nordik, J. H. J. Comput.-Aided Mol. Design 2000, 14, 123-134.