Is it possible to synthesize a low-valent transition metal complex with a neutral carbon atom as terminal ligand? A theoretical study of (CO)4FeC

Organometallics

Volumn 19, Issue 14, 2000, Pages 2698-2706

  Chen, Yu ^a   Petz, Wolfgang ^a   Frenking, Gernot ^a  

^a PHILIPPS UNIVERSITY MARBURG   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

ATOMS; CARBON; CHEMICAL BONDS; DISSOCIATION; ELECTRON ENERGY LEVELS; ELECTRONIC DENSITY OF STATES; ELECTRONIC STRUCTURE; NUMERICAL METHODS; POTENTIAL ENERGY; QUANTUM THEORY; SYNTHESIS (CHEMICAL); TRANSITION METALS;

ELECTRON DENSITY DISTRIBUTION; LEWIS ACID; LOW VALENT TRANSITION METAL COMPLEX; NEUTRAL CARBON ATOM; TOPOLOGICAL ANALYSIS;

ORGANOMETALLICS;

EID: 0034224475     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om000250o     Document Type: Article

References (70)

1. Elschenbroich, Ch.; Salzer, A. Organometallics, 2nd ed., VCH: Weinheim, 1992; p 1.
2. Fischer, E. O.; Maasböl, A. Angew. Chem. 1964, 76, 645; Angew. Chem., Int. Ed. Engl. 1964, 3, 580.
3. Fischer, E. O.; Maasböl, A. Angew. Chem. 1964, 76, 645; Angew. Chem., Int. Ed. Engl. 1964, 3, 580.
4. Schrock, R. R. J. Am. Chem. Soc. 1974, 96, 6796.
5. Fischer, E. O.; Kreis, G.; Kreiter, C. G.; Müller, J.; Huttner, G.; Lorenz, H. Angew. Chem. 1973, 85, 618; Angew. Chem., Int. Ed. Engl. 1973, 12, 564.
6. Fischer, E. O.; Kreis, G.; Kreiter, C. G.; Müller, J.; Huttner, G.; Lorenz, H. Angew. Chem. 1973, 85, 618; Angew. Chem., Int. Ed. Engl. 1973, 12, 564.
7. McLain, S. J.; Wood, C. D.; Messerle, L. W.; Schrock, R. R.; Hollander, F. J.; Youngs, W. J.; Churchill, M. R. J. Am. Chem. Soc. 1978, 100, 5962.
8. (a) Dötz, K. H.; Fischer, H.; Hofmann, P.; Kreissl, F. R.; Schubert, U.; Weiss, K. Transition Metal Carbene Complexes; Verlag Chemie: Weinheim, 1983.
9. (b) Dötz, K. H. Pure Appl. Chem. 1983, 55, 1689.
10. (c) Dötz, K. H. Angew. Chem. 1984, 96, 573; Angew. Chem., Int. Ed. Engl. 1984, 23, 587.
11. (c) Dötz, K. H. Angew. Chem. 1984, 96, 573; Angew. Chem., Int. Ed. Engl. 1984, 23, 587.
12. (d) Hegedus, L. S. Pure Appl. Chem. 1990, 62, 691.
13. (e) Fischer, H.; Hofmann, P.; Kreissl, F. R.; Schrock, R. R.; Schubert, U.; Weiss, K. Carbyne Complexes; VCH: New York, 1988.
14. (f) Transition Metal Carbyne Complexes; Kreissl, F. R., Ed.; Kluwer Academic Publishers: Dordrecht, The Netherlands, 1993.
15. (g) Mayr, A; Hoffmeister, H. Adv. Organomet. Chem. 1991, 32, 227.
16. (h) Kim, H. P.; Angelici, R. J. Adv. Organomet. Chem. 1987, 27, 51.
17. (i) Nugent, W. A.; Mayer, J. M. Metal-Ligand Multiple Bonds; Wiley: New York, 1988.
18. (a) Taylor, T. E.; Hall, M. B. J. Am. Chem. Soc. 1984, 106, 1576.
19. (b) Carter, E. A.; Goddard, W. A., III. J. Am. Chem. Soc. 1986, 108, 4746.
20. Hofmann, P. In ref 6a, p 59f.
21. (a) Vyboishchikov, S. F.; Frenking, G. Chem. Eur. J. 1998, 4, 1428.
22. (b) Vyboishchikov, S. F.; Frenking, G. Chem. Eur. J. 1998, 4, 1439.
23. (a) Chisholm, M. H.; Hammond, C. E.; Johnston, V. J.; Streib, W. E.; Huffman, J. C. J. Am. Chem. Soc. 1992, 114, 7056.
24. (b) Caulton, K. G.; Cayton, R. H.; Chisholm, M. H.; Huffman, J. C.; Lobkovsky, E. B.; Xue; Z. Organometallics 1992, 11, 321.
25. (c) Miller, R. L.; Wolczanski, P. T.; Rheingold, A. L. J. Am. Chem. Soc. 1993, 115, 10422.
26. (d) Neithamer, D. R.; LaPointe, R. E.; Wheeler, R. A.; Richeson, D. S.; Van Duyne, G. D.; Wolczanski, P. T. J. Am. Chem. Soc. 1989, 111, 9056.
27. (e) Mansuy, D.; Lecomte, J.-P.; Chottard, J.-C.; Bartoli, J.-F. Inorg. Chem. 1981, 20, 3119.
28. (f) Goedkin, V. L.; Deakin, M. R.; Bottomley, L. A. J. Chem. Soc., Chem. Commun. 1982, 607.
29. (g) Latesky, S. L.; Selegue, J. P. J. Am. Chem. Soc. 1987, 109, 4731.
30. (h) Etienne, M.; White, P. S.; Templeton, J. L. J. Am. Chem. Soc. 1991, 113, 2324.
31. Peters, J. C.; Godom, A. L.; Cummins, C. C. J. Chem. Soc., Chem. Commun. 1997, 1995.
32. Petz, W.; Weller, F. Organometallics 1993, 12, 4056.
33. 4 and the unpaired electrons of carbon in the triplet ground state. This leads to an iron atom in the formal oxidation state +2 and a carbon ligand with the formal charge -2, which is a rather unrealistic view.
34. Reed, A. E.; Curtiss, L. A.; Weinhold, F. Chem. Rev. 1988, 88, 899.
35. Bader, R. F. W. Atoms in Molecules. A Quantum Theory; Oxford Press: Oxford, 1990.
36. Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
37. Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. 1988, B37, 785.
38. Stevens, P. J.; Devlin, F. J.; Chablowski, C. F.; Frisch, M. J. J. Phys. Chem. 1994, 98, 11623.
39. Hay, P. J.; Wadt, W. R. J. Chem. Phys. 1985, 82, 299.
40. Bergner, A.; Dolg, M.; Küchle, W.; Stoll, H.; Preuss, H. Mol. Phys. 1993, 80, 1431.
41. (a) Ditchfield, R ; Hehre, W. J.; Pople, J. A. J. Chem. Phys. 1971, 54, 724.
42. (b) Hehre, W. J.; Ditchfield, R.; Pople, J. A. J. Chem. Phys. 1972, 56, 2257.
43. Frenking, G.; Antes, I.; Böhme, M.; Dapprich, S.; Ehlers, A. W.; Jonas, V.; Neuhaus, A.; Otto, M.; Stegmann, R.; Veldkamp, A.; Vyboishchikov, S. F. Reviews in Computational Chemistry, Vol. 8; Lipkowitz, K. B., Boyd, D. B., Eds.; VCH: New York, 1996; pp 63-144.
44. Cizek, J. J. Chem. Phys. 1966, 45, 4256.
45. Pople, J. A.; Krishnan, R.; Schlegel, H. B.; Binkley, J. S. Int. J. Quantum Chem. 1978, 14, 545. Bartlett, R. J.; Purvis, G. D. Int. J. Quantum Chem. 1978, 14, 561. Purvis, G. D.; Bartlett, R. J. J. Chem. Phys. 1982, 76, 1910. Purvis, G. D.; Bartlett, R. J. J. Chem. Phys. 1987, 86, 7041. Pople, J. A.; Head-Gordon, M.; Raghavachari, K. J. Chem. Phys. 1987, 87, 5968.
46. Pople, J. A.; Krishnan, R.; Schlegel, H. B.; Binkley, J. S. Int. J. Quantum Chem. 1978, 14, 545. Bartlett, R. J.; Purvis, G. D. Int. J. Quantum Chem. 1978, 14, 561. Purvis, G. D.; Bartlett, R. J. J. Chem. Phys. 1982, 76, 1910. Purvis, G. D.; Bartlett, R. J. J. Chem. Phys. 1987, 86, 7041. Pople, J. A.; Head-Gordon, M.; Raghavachari, K. J. Chem. Phys. 1987, 87, 5968.
47. Pople, J. A.; Krishnan, R.; Schlegel, H. B.; Binkley, J. S. Int. J. Quantum Chem. 1978, 14, 545. Bartlett, R. J.; Purvis, G. D. Int. J. Quantum Chem. 1978, 14, 561. Purvis, G. D.; Bartlett, R. J. J. Chem. Phys. 1982, 76, 1910. Purvis, G. D.; Bartlett, R. J. J. Chem. Phys. 1987, 86, 7041. Pople, J. A.; Head-Gordon, M.; Raghavachari, K. J. Chem. Phys. 1987, 87, 5968.
48. Pople, J. A.; Krishnan, R.; Schlegel, H. B.; Binkley, J. S. Int. J. Quantum Chem. 1978, 14, 545. Bartlett, R. J.; Purvis, G. D. Int. J. Quantum Chem. 1978, 14, 561. Purvis, G. D.; Bartlett, R. J. J. Chem. Phys. 1982, 76, 1910. Purvis, G. D.; Bartlett, R. J. J. Chem. Phys. 1987, 86, 7041. Pople, J. A.; Head-Gordon, M.; Raghavachari, K. J. Chem. Phys. 1987, 87, 5968.
49. Pople, J. A.; Krishnan, R.; Schlegel, H. B.; Binkley, J. S. Int. J. Quantum Chem. 1978, 14, 545. Bartlett, R. J.; Purvis, G. D. Int. J. Quantum Chem. 1978, 14, 561. Purvis, G. D.; Bartlett, R. J. J. Chem. Phys. 1982, 76, 1910. Purvis, G. D.; Bartlett, R. J. J. Chem. Phys. 1987, 86, 7041. Pople, J. A.; Head-Gordon, M.; Raghavachari, K. J. Chem. Phys. 1987, 87, 5968.
50. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A.; Stratmann, R. E.; Burant, J. C.; Dapprich. S.; Milliam, 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.; Gomberts, R.; Martin, R. L.; Fox, D. J.; Keith, T. A.; 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.
51. Stanton, J. F.; Gauss, J.; Watts, J. D.; Lauderdale, W. J.; Bartlett, R. J. ACES II, an ab initio program system; University of Florida: Gainesville, FL, 1991.
52. Werner, H.-J.; Knowles, P. J. Users's Manual for MOLPRO; University of Sussex, Sussex, UK, 1991.
53. Albright, T. A.; Burdett, J. K.; Whangbo, M. H. Orbital Interactions in Chemistry; Wiley: New York, 1985; pp 320-325.
54. Drouin, B. J.; Kukolich, S. G. J. Am. Chem. Soc. 1999, 121, 4023.
55. Braga, D.; Grepioni F.; Orpen, A. G. Organometallics 1993, 12, 1481.
56. Beste, A.; Krämer, O.; Gerhard, A.; Frenking, G. Eur. J. Inorg Chem. 1999, 2037.
57. Li, J.; Schreckenbach, G.; Ziegler, T. J. Am. Chem. Soc. 1995, 117, 486.
58. Barnes, L. A.; Rosi, M.; Bauschlicher, C. W., Jr. J. Chem. Phys. 1991, 94, 2031.
59. Poliakoff, M.; Weitz, E. Acc. Chem. Res. 1987, 20, 408.
60. Lewis, K. E.; Golden, D. M.; Smith, G. P. J. Am. Chem. Soc. 1984, 106, 3905.
61. Hoffmann, R. Angew. Chem. 1982, 94, 725; Angew. Chem., Int. Ed. Engl. 1982, 27, 711.
62. Hoffmann, R. Angew. Chem. 1982, 94, 725; Angew. Chem., Int. Ed. Engl. 1982, 27, 711.
63. 1D state at the one-determinant level.
64. Moore, C. E. Atomic Energy Levels. Nat. Stand. Ref. Data Ser., Nat. Bur. Stand. (U.S.) 1971. 35/V.
65. Wiberg, K. B. Tetrahedron 1968, 24, 1083.
66. The calculated small positive charge of the carbon atom in 1a does not contradict the classification of the carbon ligand as a nucleophile. Carbon monoxide also reacts as a C-nucleophilic agent, although the carbon atom of CO carries a positive charge. The shape of the charge distribution has a stronger influence on the chemical reactivity than the atomic partial charge.
67. Page 290 in ref 15.
68. Cremer, D.; Kraka, E. Angew. Chem. 1984, 96, 612; Angew. Chem., Int. Ed. Engl. 1984, 23, 627.
69. Cremer, D.; Kraka, E. Angew. Chem. 1984, 96, 612; Angew. Chem., Int. Ed. Engl. 1984, 23, 627.
70. 3.