Density functional study on the mechanism of the C-X (X = Sn, Ge, Si, C, H) σ Bond oxidative addition of HC≡CR (R = SnH3, GeH3, SiH3, CH3, H) to the (PH3)2M (M = Ni, Pd, Pt) complexes. Does the substrate approach the metal in a parallel or perpendicular manner?

Organometallics

Volumn 21, Issue 21, 2002, Pages 4482-4489

  Matsubara, Toshiaki ^a,b   Hirao, Kazuyuki ^b  

^a INSTITUTE FOR FUNDAMENTAL CHEMISTRY   (Japan)

^b KYOTO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ACTIVATION ANALYSIS; CHEMICAL BONDS; MOLECULES; POTENTIAL ENERGY; PROBABILITY DENSITY FUNCTION; SUBSTRATES;

ENERGY BARRIER;

COMPLEXATION;

EID: 0038336919     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om020208o     Document Type: Article

References (35)

1. For example, see: (a) Muetterties, E. L.; Rhodin, T. N.; Band, E.; Brucker, C. F.; Pretzer, W. R. Chem. Rev. 1979, 79, 91.
2. (b) Shilov, A. E. The Activation of Saturated Hydrocarbons by Transition Metal Complexes; D. Reidel: Dordrecht, The Netherlands, 1984.
3. (c) Crabtree, R. H. Chem. Rev. 1985, 85, 245.
4. (d) Cotton, F. A.; Wilkinson, G. In Advanced Inorganic Chemistry, 5th ed.; Wiley: New York, 1988.
5. (e) Crabtree, R. H. In The Organometallic Chemistry of the Transition Metals, 2nd ed.; Wiley: New York, 1994.
6. For example, see: (a) Koga, N.; Morokuma, K. Chem. Rev. 1991, 91, 823.
7. (b) Hay, P. J. In Transition Metal Hydrides; Dedieu, A., Ed.; VCH: New York, 1992.
8. (c) Siegbahn, P. E. M.; Blomberg, M. R. A. In Theoretical Aspects of Homogeneous Catalysis; van Leeuwen, P. W. N. M., Morokuma, K., van Lenthe, J. H., Eds.; Kluwer Academic Publishers: Dordrecht, The Netherlands, 1995.
9. (d) Musaev, D. G.; Morokuma, K. In Advances in Chemical Physics; Prigogine, I., Rice, S. A., Eds.; Wiley: New York, 1996; Vol. XCV
10. (a) Low, J. J.; Goddard, W. A., III, J. Am. Chem. Soc. 1984, 206, 6928.
11. (b) Obara, S.; Kitaura, K.; Morokuma, K. J. Am. Chem. Soc. 1984, 106, 7482.
12. (a) Low, J. J.; Goddard, W. A., III. J. Am. Chem. Soc. 1984, 106, 8321.
13. (b) Low, J. J.; Goddard, W. A., III. Organometallics 1986, 5, 609.
14. (c) Low, J. J.; Goddard, W. A., III. J. Am. Chem. Soc. 1986, 108, 6115.
15. Sakaki, S.; Mizoe, N.; Musashi, Y.; Biswas, B.; Sugimoto, M. J. Phys. Chem. A 1998, 102, 8027.
16. Mataubara, T.; Hirao, K. Organometallics 2002, 21, 2662.
17. Sahnoun, R.; Matsubara, T.; Yamabe, T. Organometallics 2000, 19, 5661.
18. For example, see: (a) Shirakawa, E.; Yoshida, H.; Hiyama, T. Tetrahedron Lett. 1997, 38, 5177.
19. (b) Shirakawa, E.; Yoshida, H.; Kurahashi, T.; Nakao, Y.; Hiyama, T. J. Am. Chem. Soc. 1998, 120, 2975.
20. (c) Shirakawa, E.; Hiyama, T. J. Organomet. Chem. 1999, 576, 169 and references therein.
21. 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; Gaussian, Inc.; Pittsburgh, PA, 1998.
22. (a) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.
23. (b) Becke, D. J. Chem. Phys. 1993, 98, 5648.
24. Ehlers, A. W.; Böhrne, M.; Dapprich, S.; Gobbi, A.; Höllwarth, A.; Jonas, V.; Köhler, K. F.; Stegmann, R.; Veldkamp, A.; Frenking, G. Chem. Phys. Lett. 1993, 208, 111.
25. Hay, P. J.; Wadt, W. R. J. Chem. Phys. 1985, 82, 299.
26. Huzinaga, S. Physical Sciences Data 16, Gaussian Basis Sets for Molecular Calculations; Elsevier: Amsterdam, 1984.
27. Wadt, W. R.; Hay, P. J. J. Chem. Phys. 1985, 82, 284.
28. Fukui, K.; Kato, S.; Fujimoto, H. J. Am. Chem. Soc. 1975, 97, 1.
29. Glendening, E. D.; Reed, A. E.; Carpenter, J. E.; Weinhold F. NBO Version 3.1.
30. (a) Saillard, J.-Y.; Hoffmann, R. J. Am. Chem. Soc. 1984, 106, 2006.
31. xy orbital is raised, with the decrease in the ∠P-M-P angle β.
32. 3, H) was as follows: for σ, Sn (-0.5007) > Ge (-0.5306) > Si (-0.5839) > H (-0.5934) > C (-0.6765); for σ*, H (0.5001) > C (0.4741) > Ge (0.3009) > Si (0.2544) > Sn (0.1843).
33. (a) Dewar, M. J. S. Bull. Soc. Chim. Fr. 1951, C71.
34. (b) Chatt, J.; Dunoanson, L. A. J. Chem. Soc. 1958, 2939.
35. 1 Therefore, the transition states were connected to the corresponding π complexes.