The carbonylation reaction of CH3Co(CO)4: A detailed density functional study

Organometallics

Volumn 21, Issue 11, 2002, Pages 2262-2267

  Goh, Sor Koon ^a   Marynick, Dennis S ^a  

^a UNIVERSITY OF TEXAS AT ARLINGTON   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYL GROUP MIGRATION;

ASSOCIATION REACTIONS; CARBONYLATION; ELECTRONS; OXYGEN; POTENTIAL ENERGY; PROBABILITY DENSITY FUNCTION;

ORGANOMETALLICS;

EID: 0002588640     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om0200297     Document Type: Article

References (57)

1. Roelen, O. (Ruhrchemie AG). D.G.B. 849 458 1938; Chem. Zentr. 1953, 927.
2. Roelen, O. (Ruhrchemie AG). D.G.B. 849 458 1938; Chem. Zentr. 1953, 927.
3. Heck, F.; Breslow, D. S. J. Am. Chem. Soc. 1961, 83, 4023.
4. Wermer, P.; Ault, B. S.; Orchin, M. J. Organomet. Chem. 1978, 162, 189.
5. Ungváry, F.; Markó, L. J. Org. Chem. 1969, 20, 205.
6. See for instance: (a) Collman, J. P.; Hegedua, L. S.; Norton, J. R.; Finke, R. G. Principles and Applications of Organotransition Metal Chemistry; University Science Books: Mill Valley, CA, 1987.
7. (b) Cotton, F. A.; Wilkinson, G. Advanced Inorganic Chemistry; Wiley: New York, 1988.
8. (a) Grima, J. P.; Choplin, F.; Kaufmann, G. J. J. Organomet. Chem. 1977, 129, 221.
9. (b) Fonnesbech, N.; Hjortkjaer, J.; Johansen, H. Int. J. Quantum Chem. 1977, 12, 95.
10. (c) Berke, H.; Hoffmann, R. J. Am. Chem. Soc. 1978, 200, 7224.
11. (d) Pensak, D. A.; McKinney, R. J. Inorg. Chem. 1979, 18, 3407.
12. (e) Eyermann, C. J.; Chung-Phillips, A. J. Am. Chem. Soc. 1984, 106, 7437.
13. (a) Veillard, A.; Strich, A. J. Am. Chem. Soc. 1988, 110, 3793.
14. (b) Daniel, C.; Hyla-Kryspin, I.; Demuynck, J.; Veillard, A. Nouv. J. Chim. 1985, 9, 581.
15. (c) Veillard, A.; Daniel, C.; Rohmer, M. M. J. Phys. Chem. 1990, 94, 5556.
16. (a) Antolovic, D.; Davidson, E. R. J. Am. Chem. Soc. 1987, 109, 977.
17. (b) Antolovic, D.; Davidson, E. R. J. Am. Chem. Soc. 1987, 209, 5828.
18. (c) Antolovic, D.; Davidsion, E. R. J. Chem. Phys. 1988, 88, 4967.
19. (a) Versluis, L.; Ziegler, T.; Baerends, E. J.; Ravenek, W. J. Am. Chem. Soc. 1989, 111, 2018.
20. (b) Versluis, L.; Ziegler, T. Organometallics 1990, 9, 2985.
21. (c) Versluis, L.; Ziegler, T. Inorg. Chem. 1990, 29, 4530.
22. (d) Versluis, L.; Ziegler, L. J. Am. Chem. Soc. 1990, 112, 6763.
23. (e) Ziegler, T. Pure Appl. Chem. 1991, 63, 873.
24. (f) Ziegler, T.; Versluis, L. Adv. Chem. Ser. 1992, No. 230, 75.
25. (g) Ziegler, T.; Cavallo, L.; Bérces, A. Organometallics 1993, 12, 3586.
26. (h) Miquel, S.; Ziegler, T. Organometallics 1996, 15, 2611.
27. Rogers, J. R.; Kwon, O.; Marynick, D. S. Organometallics 1991, 10, 2816.
28. Slater, J. C. Adv. Quantum Chem. 1972, 6, 1. Baerends, E. J.; Ellis, D. E.; Ros, P. Chem. Phys. 1973, 2, 41.
29. Slater, J. C. Adv. Quantum Chem. 1972, 6, 1. Baerends, E. J.; Ellis, D. E.; Ros, P. Chem. Phys. 1973, 2, 41.
30. (a) Salem, L. In Electrons in Chemical Reactiions; Wiley: New York, 1982.
31. (b) Komornicki, A.; Mclver, J. W. J. Am. Chem. Soc. 1974, 96, 5798.
32. Derecskei-Kovacs, A.; Marynick, D. S. J. Am. Chem. Soc. 2000, 122, 2078.
33. (a) Werner, H. J.; Knowles, P. J. J. Chem. Phys. 1985, 82, 5053.
34. (b) Knowles, P. J.; Werner, H. J. Chem. Phys. Lett. 1985, 115, 259.
35. (c) Werner, H. J.; Knowles, P. J. MOLPRO; University of Sussex, 1991.
36. Frenking, G.; Antes, I; Boehme, M.; Dapprich, S.; Ehlers, A. W.; Jonas, V.; Nehaus, A.; Otto, M.; Stegmann, R.; Veldjamp, A.; Vyboishehikov, S. F. In Reviws in Computational Chemistry, Lipkowitz, K. B., Boyd, D. B., Eds.; VCH: New York, 1996; Vol. 8, p 63.
37. Torrent, M.; Gili, P.; Duran, M.; Solà, M. J. Chem. Phys. 1996, 104, 9499.
38. (a) Bauschlicher, C. W.; Ricca, A.; Partridge, H.; Langhoff, S. R. In Recent Advances in Density Functional Theory; Chong, D. P., Ed.; World Scientific: Singapore, 1997; Part II.
39. (b) Siegbahn, P. E. M. Electronic Calculations for Molecules Containing Transition Metals. Adv. Chem. Phys. 1996, XCIII.
40. (c) Pavlov, M.; Siegbahn, P. E. M.; Sandstrm, M. J. Phys. Chem. A 1998, 102, 219.
41. (d) Filatov, M.; Shaik, S. J. Phys. Chem. A 1998, 102, 3835.
42. (a) Becke, A. D. J. Chem. Phys. 1993, 95, 5648.
43. (b) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.
44. 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.1; Gaussian, Inc.: Pittsburgh, PA, 1998.
45. (a) Wachters, A. J. H. J. Chem. Phys. 1970, 52, 1033.
46. (b) Hay, P. J. J. Chem. Phys. 1977, 66, 4377.
47. Hariharan, P. C.; Pople, J. A. Theor. Chim. Acta 1973, 28, 213.
48. Sweany, R. L.; Russell, F. N. Organometallics 1988, 7, 719.
49. Rossi, A. R.; Hoffmann, R. Inorg. Chem. 1975, 14, 365.
50. For comparison, we have also calculated the energetics of all structures at the BP86 level using the B3LYP geometries (BP86//B3LYP). The calculated energetics (in kcal/mol, without ZPE corrections) are as follows: 1a (0.0), 1b (8.4), 1c (8.8), 1d (3.3), 1e (5.3), 1f (1.0), 1g (9.9), 1h (13.7), 2a (6.3), 2b (10.8), 2c (1.1), 2d (8.3) and 2e (-23.0). Excluding 2e, the two approaches agree to within an average absolute error of 2.0 kcal/mol. However, BP86 predicts the AB of the overall carbonylation reaction (which corresponds to the energy of 2e) to be 9.2 kcal/mol more exoergic than B3LYP. While the experimental value is not known, our earlier study of the carbonylation of pentacarbonyl(methyl)manganese(I) showed very similar behavior. In that case, the experimental value was known, and the calculated value using the B3LYP functional was in much better agreement with experiment. For this reason, we have used the B3LYP energetics as the basis of the mechanistic discussions in what follows.
51. 2. See: Koga, N.; Jin, S. Q.; Morokuma, K. J. Am. Chem. Soc. 1988, 110, 3417. Matsubara, T.; Koga, N.; Ding, J.; Musaev, D. G.; Morokuma, K. Organometallics 1997, 16, 1065.
52. 2. See: Koga, N.; Jin, S. Q.; Morokuma, K. J. Am. Chem. Soc. 1988, 110, 3417. Matsubara, T.; Koga, N.; Ding, J.; Musaev, D. G.; Morokuma, K. Organometallics 1997, 16, 1065.
53. These plots were obtained with Spartan 5.0 (Wavefunction, Inc., Irving, CA).
54. Nagy-Magos, Z.; Bor, G.; Markó, L. J. Organomet. Chem. 1968, 14, 205.
55. DeMore, W. B.; Sander, S. P.; Howard, C. J.; Ravinsshankara, A. R.; Golden, D. M.; Kolb, C. E.; Hampson, H. F.; Kurylo, M. J.; Molina, M. J, Chemical Kinetics and Photochemical Data for Use in Stratospheric Modeling; Evaluation Number 12, Jet Propulsion Laboratory, 1997.
56. Gerrard, W. Solubility of Gases and Liquids; Plenum Press: New York, London, 1976.
57. 3 bonding orbital with the appropriate in-plane LUMO.