Electron density of semi-bridging carbonyls. Metamorphosis of CO ligands observed via experimental and theoretical investigations on [FeCo(CO)8]-

Journal of the American Chemical Society

Volumn 124, Issue 47, 2002, Pages 14173-14184

  Macchi, Piero ^a,b   Garlaschelli, Luigi ^a   Sironi, Angelo ^a,b  

^a UNIVERSITY OF MILAN   (Italy)

^b CNR   (Italy)

Author keywords

[No Author keywords available]

Indexed keywords

CARBON MONOXIDE; CARBONYLATION; CONFORMATIONS; DIMERS; TRANSITION METALS; X RAY DIFFRACTION;

INTERATOMIC DELOCALIZATION INDEXES;

CARRIER CONCENTRATION;

CARBON MONOXIDE; CARBONYL DERIVATIVE; DIMER; IRON DERIVATIVE; LIGAND;

ARTICLE; CHEMICAL STRUCTURE; DENSITY; ELECTRON; MATHEMATICAL COMPUTING; MOLECULAR INTERACTION; QUANTUM CHEMISTRY; QUANTUM THEORY; X RAY DIFFRACTION;

EID: 2242492682     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja026186e     Document Type: Article

References (81)

1. Gade, L. H. Angew. Chem., Int. Ed. 2000, 39, 2658-2678, and references therein.
2. Powell, M. H.; Ewens, R. V. G. J. Chem. Soc. 1939, 286-292.
3. Dahl, L. F.; Rundle, R. E. Acta Crystallogr. 1963, 16, 419-426.
4. Noteworthy, also the covalent/electrostatic nature of the M-CO interaction in mononuclear complexes is still a matter of discussion; see Frenking, G.; Fröhlich, N. Chem. Rev. 2000, 100, 717-774, and references therein.
5. Bauschlicher, C. W. J. Chem. Phys. 1986, 84, 872-875.
6. Sironi, A. Metal Clusters in Chemistry; Braunstein, Oro, Raithby, Eds.; Wiley-VCH: New York, 1999; Vol. 2, 937-959, and references therein.
7. Cambridge Crystallographic Data Centre, June 2001.
8. A similar picture has been previously reported by Orpen, A. G. Chem. Soc. Rev. 1993, 22, 191-197.
9. Heijser, W.; Baerends, E. J.; Ros, P. Faraday Symp. 1980, 14, 211-234.
10. (a) Bauschlicher, C. W. J. Chem. Phys. 1986, 84, 872-875.
11. (b) Summerville, R. H.; Hoffmann, R. J. Am. Chem. Soc. 1979, 101, 3821-3831.
12. Mealli, C.; Proserpio, D. M. J. Organomet. Chem. 1990, 386, 203-208.
13. Martin, M.; Rees, B.; Mitschler, A. Acta Crystallogr. 1982, B38, 6-15.
14. Hall, M. B. In Electron Distribution and the Chemical Bond; Coppens, P., Hall, M. B., Eds.; Plenum Press: New York, 1982; p 205.
15. Brown, D. A.; Chambers, W. J.; Fitzpatrick, N. J.; Rawilson, R. M. J. Chem. Soc. A 1971, 720-725.
16. Bader, R. F. W. Atoms in Molecules. A Quantum Theory; Cambridge University Press: Oxford U.K., 1991.
17. Macchi, P.; Proserpio, D. M.; Sironi, A. J. Am. Chem. Soc. 1998, 120, 13 429-13 435.
18. Bianchi, R.; Gervasio, G.; Marabello, D. Chemm. Commun. 1998, 1535-1536.
19. Macchi, P.; Garlaschelli, L.; Martinengo, S.; Sironi, A. J. Am. Chem. Soc. 1999, 121, 10 428-10 429.
20. (a) Low, A. A.; Kunze, K. L.; MacDougall, P. J.; Hall, M. B. Inorg. Chem. 1991, 30, 1079-1086.
21. (b) Bo, C.; Sarasa, J. P.; Poblet, J. M. J Phys. Chem. 1993, 97, 6362-6366.
22. Bürgi, H.-B. Angew. Chem. 1975, 87, 461-475.
23. Chin, H. B.; Smith, M. B.; Wilson, R. D.; Bau, R. J. Am. Chem. Soc. 1974, 96, 5285-5287.
24. 2 = 0.1167). Atomic coordinates and principal distances and angles are included in the Supporting Information.
25. Sheldrick, G. M. 1996 SADABS, University of Göttingen, Germany, unpublished.
26. Farrugia, L. J. J. Appl. Crystallogr. 1999, 32, 837-838.
27. Sheldrick, G. M. SHELX-97: A Program for Structure Refinement. University of Gottingen, Germany.
28. 2 = 0.0787 vs. 0.0825.
29. eq).
30. P. Macchi, 2000, unpublished results.
31. Koritsanszky, T.; Howard, S. T.; Su, Z.; Mallinson, P. R.; Richter, T.; Hansen, N. K. XD, Computer Program Package for Multipole refinement and Analysis of Electron Densities from Diffraction Data, Free University of Berlin, Germany, June 1997.
32. Hansen, N. K.; Coppens, P. Acta Crystallogr. Sect. A 1978, 34, 909-921.
33. (a) Su, Z.; Coppens, P. Acta Crystallogr. 1998, A54, 646-652.
34. (b) Macchi, P.; Coppens, P. Acta Crystallogr. 2001, A57, 656-662.
35. Stewart, R. F.; Bentley, J.; Goodman, B. J. Chem. Phys. 1975, 63, 3786-3793.
36. Clementi, E.; Raimondi, D. L. J. Chem. Phys. 1963, 38, 2686-2689. For sp shell, the exponents of 2s and 2p orbitals are simply averaged.
37. Abramov, Y.; Volkov, A.; Coppens, P. Chem. Phys. Lett. 1999, 311, 81-86.
38. 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.
39. Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
40. Hay, P. J.; Wadt, W. R. J. Chem. Phys. 1985, 82, 299.
41. Dunning, T. H.; Hay, P. J. Modern Theoretical Chemistry: Schaefer, H. F., III, Ed.; Plenum: New York, 1976, 3, 1.
42. Biegler-König, F. W.; Bader, R. F. W.; Ting-Hua, T. J. Comput. Chem. 1982, 3, 317-328.
43. Biegler-König, F. W. AIM2000, version 1.0, University of Applied Sciences, Bielefeld, Germany.
44. Popelier, P. L. A. Comput. Phys. Commun. 1996, 93, 212-240; Popelier, P. L. A. Chem. Phys. 1994, 228, 160-164.
45. Popelier, P. L. A. Comput. Phys. Commun. 1996, 93, 212-240; Popelier, P. L. A. Chem. Phys. 1994, 228, 160-164.
46. Girones, X.; Ponec, R.; Roithova. J. Program WBader, version 1.0. 2001.
47. Bridgeman, A. J.; Cavigliasso, G.; Ireland, L. R.; Rothery, J. J. Chem. Soc., Dalton Trans. 2001, 2095-2108.
48. Macchi, P.; Sironi, A., Coord. Chem. Rev., in press.
49. Rosa, A.; Ehlers, A. W.; Baerends, E. J.; Snijders, J. G.; te Velde, G. J. Phys. Chem. 1996, 100, 5690-5696.
50. Jonas, V.; Frenking, G.; Reetz, M. T. J. Am. Chem. Soc. 1994, 116, 8741-8753.
51. However, there is no substantial difference in the Fe-Co distance.
52. Martin, A.; Orpen, A. G. J. Am. Chem. Soc. 1996, 118, 1464-1470.
53. Coppens, P.; Becker, P. J. International Tables for Crystallography, 1995, Vol. C, 628.
54. A chemical bond is associated with a line of maximum electron density, called the bond path (bp), which connects two bonded atoms. The atoms are characterised as maxima of ρ and are defined in space by an atomic basin. A saddle point of ρ
55. b).
56. 2ρ (see also ref 16)
57. Molina-Molina, J.; Dobado, J. A.; Heard, L.; Bader, R. F. W.; Sundberg, M. R. Ther. Chem. Acc. 2001, 105, 365-373.
58. bcp) increases as the interatomic surface lies closer to an atomic core, thus it grows with the bond order in homopolar interactions due to the smaller inter-nuctear separations (see for example the series C-C, C=C, and C≡C in Table 3) and in polar interactions because the interatomic surface is particularly penetrated into the atomic core of the electropositive atom.
59. Bader, R. F. W.; Stephens, M. E. J. Am. Chem. Soc. 1975, 97, 7391-7399. Through a partitioning of the pair density distribution a localisation index (number of electron pairs localised inside an atomic basin) and a delocalisation index (number of electron pairs delocalised between two atoms, hereinafter δ(A, B)) are defined. At the HF level of theory, δ(A, B) are in almost exact agreement with the Lewis theory, whereas post-HF correlated calculations show some significant reduction of the bonded electron pairs compared to the expectations of electron counting rules ((b) Fradera. X.; Austen, M. A.; Bader R. F. W. J. Phys. Chem. A 1999, 103, 304-314). By its definition δ(A, B) is not restricted to atoms sharing a common interatomic surface and therefore is an indicator able to depict the "electronic communication" between atoms.
60. Bader, R. F. W.; Stephens, M. E. J. Am. Chem. Soc. 1975, 97, 7391-7399. Through a partitioning of the pair density distribution a localisation index (number of electron pairs localised inside an atomic basin) and a delocalisation index (number of electron pairs delocalised between two atoms, hereinafter δ(A, B)) are defined. At the HF level of theory, δ(A, B) are in almost exact agreement with the Lewis theory, whereas post-HF correlated calculations show some significant reduction of the bonded electron pairs compared to the expectations of electron counting rules ((b) Fradera. X.; Austen, M. A.; Bader R. F. W. J. Phys. Chem. A 1999, 103, 304-314). By its definition δ(A, B) is not restricted to atoms sharing a common interatomic surface and therefore is an indicator able to depict the "electronic communication" between atoms.
61. Mayer, I. Chem. Phys. Lett. 1983, 97, 270-274; Mayer, I. Int. J. Quantum Chem. 1984, 26, 151-154.
62. Mayer, I. Chem. Phys. Lett. 1983, 97, 270-274; Mayer, I. Int. J. Quantum Chem. 1984, 26, 151-154.
63. Li-Li bond is excluded here because the density is characterised by nonnuclear maximum in the middle of the bond (Gatti, C.; Fantucci, P.; Pacchioni, G.; Theor. Chim. Acta (Berlin) 1987, 72, 433-458).
64. Davidson, E. R.; Kunze, K. L.; Machado, F. B. C.; Chakravorty, S. J. Acc. Chem. Res. 1993, 26, 628-635.
65. Kenny, J. P.; King, R. B.; Schaefer, H. F. Inorg. Chem. 2001, 40, 900-911.
66. Aullón, G.; Alvarez, S. Eur. J. Inorg. Chem. 2001, 3031-3038.
67. Leung, P. C.; Coppens, P. Acta Crystallogr. 1983, B39, 535-542.
68. (a) Petz, W.; Weller, F. Z. Kristallogr.-New Crystal Structures 1997, 212, 157-158.
69. (b) Bhattacharyya, N. K.; Coffy, T. J.; Quintana, W.; Salupo, T. A.; Bricker, J. C.; Shay, T. B.; Payne, M.; Shore, S. G. Organometallics 1990, 9, 2368-2374.
70. (c) Cassidy, J. M.; Whitmire, K. H.; Long G. J. J. Organomet. Chem. 1992, 427, 355-362.
71. (d) Bockman, T. M.; Cho, H.-C.; Kochi, J. K. Organometallics 1995, 14, 5221-5231.
72. 2v isomer (which is not a minimum in the gas phase) has been observed in the strong polarising environment produced by Li cations (Neumuller, B.; Petz, W. Organometallics 2001, 20, 163-170.
73. -, the coordination III is not associated to a stable isomer, since the corresponding equilibrium geometries have at least one imaginary frequency. However, the theoretical observation that symmetric bridges quench the MM bond path is well supported in many analogous fragments.
74. 4 moiety.
75. Hoffmann, R. Acc. Chem. Res. 1971, 4, 1-9.
76. 8, where 1,3 Co - - - C delocalisation is found even with the axial carbonyls. Given the relatively large distortion of the bond path at Co (see angle β) even for those conformations where a direct Fe-C(1) is absent, the Co-C(1) interaction could be carrier of the through bond mechanism. In fact, the observed β > α1 and β > γ are justified only if we consider a "CO-insertion" into the M-M direct coupling (a direct Fe-C(1) coupling would not affect β).
77. Uhl, W.; Melle, S.; Frenking, G.; Hartmann, M. Inorg. Chem. 2001, 40, 750-755.
78. Uhl, W.; Pohlmann, M.; Wartchow, R. Angew. Chem., Int. Ed. 1998, 37, 961-963.
79. Bianchi, R.; Gervasio, G.; Marabello, D. Helv. Chim. Acta. 2001, 84, 722-734.
80. Larger than those of terminal carbonyls and free CO.
81. Abramov, Y. A. Acta Crystallogr. 1997, A53, 264-272.