The nature of the transition metal-carbonyl bond and the question about the valence orbitals of transition metals. A bond-energy decomposition analysis of TM(CO)6(q) (TM(q) = Hf2-, Ta-, W, Re+, Os2+, Ir3+)

Journal of the American Chemical Society

Volumn 122, Issue 27, 2000, Pages 6449-6458

  Diefenbach, Axel ^a   Bickelhaupt, F Matthias ^b   Frenking, Gernot ^a  

^a PHILIPPS UNIVERSITY MARBURG   (Germany)

^b VU UNIVERSITY AMSTERDAM   (Netherlands)

Author keywords

[No Author keywords available]

Indexed keywords

CARBONYL DERIVATIVE; METAL DERIVATIVE;

ARTICLE; CHEMICAL BOND; DISSOCIATION; ENERGY TRANSFER; LIGAND BINDING; METAL BINDING; QUANTUM CHEMISTRY; REACTION ANALYSIS;

EID: 0034641227     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja000663g     Document Type: Article

References (108)

1. Heitler, W.; London, F. Z. Physik, 1927, 44, 455.
2. (a) Fukui, K. Acc. Chem. Res. 1971, 4, 57.
3. (b) Fleming, I. Frontier Orbitals and Organic Chemical Reactions; Wiley: New York, 1976.
4. Kutzelnigg, W. Angew. Chem. 1984, 96, 262; Angew. Chem., Int. Ed. Engl. 1984, 23, 272.
5. Kutzelnigg, W. Angew. Chem. 1984, 96, 262; Angew. Chem., Int. Ed. Engl. 1984, 23, 272.
6. (a) Schmidt, M. W.; Truong, P. N.; Gordon, M. S. J. Am. Chem. Soc. 1987, 109, 5217.
7. (b) Jacobsen, H.; Ziegler, T. J. Am. Chem. Soc. 1994, 116, 3667.
8. (a) Reed, A.; Schleyer, P.v. R. J. Am. Chem. Soc. 1990, 112, 1434.
9. (b) Magnusson, E. J. Am. Chem. Soc. 1990, 112, 7940.
10. (c) Cioslowski, J.; Mixon, S. T. Inorg. Chem. 1993, 32, 3209.
11. (d) Cooper, D. L.; Cunningham, T. P.; Gerratt, J.; Karadakov, P. B.; Raimondi, M. J. Am. Chem. Soc. 1994, 116, 4414.
12. (e) Häser, M. J. Am. Chem. Soc. 1996, 118, 7311.
13. (f) Dobado, J. A.; Martinez-Garcia, H.; Molina, J. M.; Sundberg, M. R. J. Am. Chem. Soc. 1998, 120, 8461.
14. (a) Hoffmann, R.; Chen, M. M. L.; Thorn, D. L. Inorg. Chem. 1977, 16, 503.
15. (b) Schilling, B. E. R.; Hoffmann, R. J. Am. Chem. Soc. 1979, 101, 3456.
16. (c) Hoffmann, R. Science (Washington, D.C.) 1981, 211, 995.
17. (d) Hoffmann, R.; Albright, T. A.; Thorn, D. L. Pure Appl. Chem. 1978, 50, 1.
18. (e) Jean, Y.; Lledos, A.; Burdett, J. K.; Hoffmann, R. J. Am. Chem. Soc. 1988, 110, 4506, and further references cited therein.
19. (a) Davidson, E. R.; Kunze, K. L.; Machado, F. B. C.; Chakravorty, S. J. Acc. Chem. Res. 1993, 26, 628.
20. (b) Baerends, E. J.; Rozendaal, A. In Quantum Chemistry: The Challenge of Transition Metals and Coordination Chemistry; Proceedings of the NATO ASI; Veillard, A., Ed; Reidel: Dordrecht, Germany, 1986; p 159.
21. (a) Dewar, M. J. S. Bull. Soc. Chim. Fr. 1951, 18, C79.
22. (b) Chatt, J.; Duncanson, L. A. J. Chem. Soc. 1953, 2929.
23. Morokuma, K. Acc. Chem. Res. 1977, 10, 294.
24. (a) Bauschlicher, C. W.; Bagus, P. S. J. Chem. Phys. 1984, 81, 5889.
25. (b) Bauschlicher, C. W.; Petterson, L. G. M.; Siegbahn, P. E. M. J. Chem. Phys. 1987, 87, 2129.
26. (c) Bauschlicher, C. W.; Langhoff, S. R.; Barnes, L. A. Chem. Phys. 1989, 129, 431.
27. (d) Bauschlicher, C. W. J. Chem. Phys. 1986, 84, 260.
28. (e) Bauschlicher, C. W.; Bagus, P. S.; Nelin, C. J.; Roos, B. O. Chem. Phys. 1986, 85, 354.
29. (f) Barnes, L. A.; Rosi, M.; Bauschlicher, C. W. J. Chem. Phys. 1991, 94, 2031.
30. (g) Barnes, L. A.; Rosi, M.; Bauschlicher, C. W. J. Chem. Phys. 1990, 93, 609.
31. (h) Barnes, L. A.; Bauschlicher, C. W. J. Chem. Phys. 1989, 91, 314.
32. (i) Blomberg, M. R. A.; Brandemark, U. B.; Siegbahn, P. E. M.; Wennerberg, J.; Bauschlicher, C. W. J. Am. Chem. Soc. 1988, 110, 6650.
33. (j) Hall, M. B.; Fenske, R. F. Inorg. Chem. 1972, 11, 1620.
34. (k) Sherwood, P. E.; Hall, M. B. Inorg. Chem. 1979, 18, 2325.
35. (l) Sherwood, P. E.; Hall, M. B. Inorg. Chem. 1980, 19, 1805.
36. (m) Williamson, R. L.; Hall, M. B. Int. J. Quantum Chem. 1987, 21S, 503.
37. (n) Hillier, I. H.; Saunders: V. R. Mol. Phys. 1971, 23, 1025.
38. (o) Hillier, I. H.; Saunders: V. R. J. Chem. Soc., Chem. Commun. 1971, 642.
39. (p) Ford, P. C.; Hillier, I. H. J. Chem. Phys. 1984, 80, 5664.
40. (q) Ford, P. C.; Hillier, I. H.; Pope, S. A.; Guest, M. F. Chem. Phys. Lett. 1983, 102, 555.
41. (r) Cooper, G.; Green, J. C.; Payne, M. P.; Dobson, B. R.; Hillier, I. H. Chem. Phys. Lett. 1986, 125, 97.
42. (s) Cooper, G.; Green, J. C.; Payne, M. P.; Dobson, B. R.; Hillier, I. H.; Vincent, M.; Rosi, M. J. Chem. Soc., Chem. Commun. 1986, 438.
43. (t) Moncrieff, D.; Ford, P. C.; Hillier, I. H.; Saunders, V. R. J. Chem. Soc., Chem. Commun. 1983, 1108.
44. (u) Smith, S.; Hillier, I. H.; von Niessen, W.; Guest, M. C. Chem. Phys. 1989, 135, 357.
45. (v) Vanquickenborne, L. G.; Verhulst, J. J. Am. Chem. Soc. 1987, 109, 4825.
46. (w) Pierfoot, K.; Verhulst, J.; Verbeke, P.; Vanquickenborne, L. G. Inorg. Chem. 1989, 28, 3059.
47. (x) Yamamoto, S.; Kashiwagi, H. Chem. Phys. Lett. 1993, 205, 306.
48. (y) Blomberg, M. R. A.; Siegbahn, P. E. M.; Lee, T. L.; Rendell, A. P.; Rice, J. E. J. Chem. Phys. 1991, 95, 5898.
49. (a) Ziegler, T.; Rauk, A. Theor. Chim. Acta 1977, 46, 1.
50. (b) Ziegler, T.; Rauk, A. Inorg. Chem. 1979, 18, 1558.
51. (c) Ziegler, T.; Rauk, A. Inorg. Chem. 1979, 18, 1755.
52. Ehlers, A. W.; Ruiz-Molares, Y.; Baerends, E. J.; Ziegler, T. Inorg. Chem. 1997, 36, 5031.
53. Selected examples: (a) Jacobsen, H.; Ziegler, T. Organometallics 1995, 14, 224. (b) Jacobsen, H.; Ziegler, T. Inorg. Chem. 1996, 35, 775. (c) Li, J.; Schreckenbach, G.; Ziegler, T. J. Am. Chem. Soc. 1995, 117, 486. (d) Ehlers, A. W.; Baerends, E. J.; Bickelhaupt, F. M.; Radius, U. Chem. - Eur. J. 1998, 4, 210.
54. Selected examples: (a) Jacobsen, H.; Ziegler, T. Organometallics 1995, 14, 224. (b) Jacobsen, H.; Ziegler, T. Inorg. Chem. 1996, 35, 775. (c) Li, J.; Schreckenbach, G.; Ziegler, T. J. Am. Chem. Soc. 1995, 117, 486. (d) Ehlers, A. W.; Baerends, E. J.; Bickelhaupt, F. M.; Radius, U. Chem. - Eur. J. 1998, 4, 210.
55. Selected examples: (a) Jacobsen, H.; Ziegler, T. Organometallics 1995, 14, 224. (b) Jacobsen, H.; Ziegler, T. Inorg. Chem. 1996, 35, 775. (c) Li, J.; Schreckenbach, G.; Ziegler, T. J. Am. Chem. Soc. 1995, 117, 486. (d) Ehlers, A. W.; Baerends, E. J.; Bickelhaupt, F. M.; Radius, U. Chem. - Eur. J. 1998, 4, 210.
56. Selected examples: (a) Jacobsen, H.; Ziegler, T. Organometallics 1995, 14, 224. (b) Jacobsen, H.; Ziegler, T. Inorg. Chem. 1996, 35, 775. (c) Li, J.; Schreckenbach, G.; Ziegler, T. J. Am. Chem. Soc. 1995, 117, 486. (d) Ehlers, A. W.; Baerends, E. J.; Bickelhaupt, F. M.; Radius, U. Chem. - Eur. J. 1998, 4, 210.
57. (a) Strauss, S. H. Chemtracts 1997, 10, 77.
58. (b) Willner, H.; Aubke, F. Angew. Chem. 1997, 109, 2506. Angew. Chem., Int. Ed. Engl. 1997, 2402.
59. (b) Willner, H.; Aubke, F. Angew. Chem. 1997, 109, 2506. Angew. Chem., Int. Ed. Engl. 1997, 2402.
60. (a) Mavridis, A.; Harrison, J. F.; Allison, J. J. Am. Chem. Soc. 1989, 111, 2482.
61. (b) Allison, J.; Mavridis, A.; Harrison, J. F. Polyhedron 1988, 7, 1559.
62. (c) Barnes, L. A.; Rosi, M.; Bauschlicher, C. W. J. Chem. Phys. 1990, 93, 609
63. (d) Bauschlicher, C. W.; Barnes, L. A. Chem. Phys. 1988, 124, 383.
64. (e) Büker, H. J.; Maitre, P.; Ohanessian, G. J. Phys. Chem. A 1997, 101, 3966.
65. (f) Lupinetti, A. J.; Jonas, V.; Thiel, W.; Strauss, S. H.; Frenking, G. Chem. Eur. J. 1999, 5, 2573.
66. (g) Veldkamp, A.; Frenking, G. Organometallics 1993, 12, 4613.
67. (h) Lupinetti, A. J.; Fau, S.; Frenking, G.; Strauss, S. H. J. Phys. Chem. A 1997, 101, 9551.
68. Szilagyi, R. K.; Frenking, G. Organometallics 1997, 16, 4807.
69. Lupinetti, A. J.; Frenking, G.; Strauss, S. H. Angew. Chem. 1998, 110, 2229; Angew. Chem., Int. Ed. Engl. 1998, 37, 2113.
70. Lupinetti, A. J.; Frenking, G.; Strauss, S. H. Angew. Chem. 1998, 110, 2229; Angew. Chem., Int. Ed. Engl. 1998, 37, 2113.
71. Dapprich, S.; Frenking, G. J. Phys. Chem. 1995, 99, 9352.
72. (a) Landis, C. R.; Cleveland, T.; Firman, T. K. J. Am. Chem. Soc. 1995, 117, 1859.
73. (b) Landis, C. R.; Firman, T. K.; Root, D. M.; Cleveland, T. J. Am. Chem. Soc. 1998, 120, 1842.
74. (c) Landis, C. R.; Cleveland, T.; Firman, T. K. J. Am. Chem. Soc. 1998, 120, 2641.
75. (d) Firman, T. K.; Landis, C. R. J. Am. Chem. Soc. 1998, 120, 12650.
76. Bayse, C. A.; Hall, M. B. J. Am. Chem. Soc. 1999, 121, 1348.
77. Becke, A. D. Phys. Rev. A: At., Mol., Opt. Phys. 1988, 38, 3098.
78. Perdew, J. P. Phys. Rev. B: Condens. Mater. 1986, 33, 8822.
79. (a) Chang, C.; Pelissier, M.; Durand, Ph. Phys. Scr. 1986, 34, 394.
80. (b) Heully, J.-L.; Lindgren, I.; Lindroth, E.; Lundquist, S.; Martensson-Pendrill, A.-M. J. Phys. B: At. Mol. Opt. Phys. 1986, 19, 2799.
81. (c) van Lenthe, E.; Baerends, E. J.; Snijders, J. G. J. Chem. Phys. 1993, 99, 4597.
82. (d) van Lenthe, E.; Baerends, E. J.; Snijders, J. G. J. Chem. Phys. 1996, 105, 6505.
83. (e) van Lenthe, E.; van Leeuwen, R.; Baerends, E. J.; Snijders, J. G. Int. J. Quantum Chem. 1996, 57, 281.
84. Snijders, J. G.; Baerends, E. J.; Vernooijs, P. At. Data Nucl. Data Tables 1982, 26, 483.
85. Baerends, E. J.; Ellis, D. E.; Ros, P. Chem. Phys. 1973, 2, 41.
86. Krijn, J.; Baerends, E. J. Fit Functions in the HFS-Method; Internal Report (in dutch); Vrije Universiteit Amsterdam: The Netherlands, 1984.
87. Hirshfeld, E. L. Theor. Chim. Acta 1977, 44, 129.
88. (a) Fonseca Guerra, C.; Snijders, J. G.; te Velde, G.; Baerends, E. J. Theor. Chem. Acc. 1998, 99, 391.
89. (b) Bickelhaupt, F. M.; Baerends, E. J. Rev. Comput. Chem., Vol. 15, in print.
90. orb makes it also possible to estimate the electrostatic and covalent contributions to the metal - CO bonding interactions.
91. Lewis, K. E.; Golden, D. M.; Smith, G. P. J. Am. Chem. Soc. 1984, 106, 3905.
92. (a) Ellis, J. E.; Chi, K.-M. J. Am. Chem. Soc. 1990, 112, 6022.
93. (b) Siebert, H. Anwendungen der Schwingungsspektroskopie in der anorganischen Chemie; Springer: Berlin, Germany, 1966.
94. (c) Jones, L. H.; McDowell, R. S.; Goldblatt, M. Inorg. Chem. 1969, 8, 2349.
95. (d) Abel, E. W.; McLean, R. A. N.; Tyfield, S. P.; Braterman, P. S.; Walker, A. P.; Hendra, P. J. J. Mol. Spectrosc. 1969, 30, 29.
96. (e) Wang, C.; Bley, B.; Balzer-Jöllenbeck, G.; Lewis, A. R.; Siu, S. C.; Willner, H.; Aubke, F. J. Chem. Soc., Chem. Commun. 1995, 2071.
97. (f) Bach, C.; Willner, H.; Wang, C.; Rettig, S. J.; Trotter, J.; Aubke, F. Angew. Chem. 1996, 108, 2104; Angew. Chem., Int Ed. Engl. 1996, 35, 1974.
98. (f) Bach, C.; Willner, H.; Wang, C.; Rettig, S. J.; Trotter, J.; Aubke, F. Angew. Chem. 1996, 108, 2104; Angew. Chem., Int Ed. Engl. 1996, 35, 1974.
99. Jonas, V.; Thiel, W. Organometallics 1998, 17, 353.
100. Elschenbroich, Ch.; Salzer, A. Organometallics, 2nd ed.; VCH: Weinheim, Germany, 1992.
101. 6 (-9.060 eV). Thus, the calculated data can be considered as an upper bound for the TM←CO π-donation.
102. Lupinetti, A. J.; Fau, S.; Frenking, G.; Strauss, S. H. J. Phys. Chem. A 1997, 101, 9551.
103. Goldman, A. S.: Krogh-Jespersen, K. J. Am. Chem. Soc. 1996, 118, 12159.
104. Please note that the orbital relaxation step gives the contributions by all s and p orbitals of the metal and not only the valence orbitals. However, the dominant contributions should come from the valence orbitals.
105. (a) Arnesen, S. V.; Seip, H. M. Acta Chem. Scand. 1966, 20, 2711.
106. (b) Calderazzo, F.; Englert, U.; Pampaloni, G.; Pelizzi, G.; Zamboni, R. Inorg. Chem. 1983, 22, 1865.
107. (c) Bruce, D. M.; Holloway, J. H.; Russel, D. R. J. Chem. Soc., Dalton Trans. 1978, 1627.
108. (d) Holloway, J. H.; Senior, J. B.; Szary, A. C. J. Chem. Soc., Dalton Trans. 1987, 741.