Dehalogenation of chloroalkenes at cobalt centers. A model density functional study

Organometallics

Volumn 26, Issue 6, 2007, Pages 1494-1504

  Bühl, Michael ^a   Vrček, Ivana Vinković ^b   Kabrede, Hendrik ^a  

^a MAX PLANCK INSTITUT FÜR KOHLENFORSCHUNG   (Germany)

^b UNIVERSITY OF ZAGREB   (Croatia)

Author keywords

[No Author keywords available]

Indexed keywords

BIOLOGICAL SYSTEMS; COBALT COMPOUNDS; DEHALOGENATION; DENSITY FUNCTIONAL THEORY; ORGANOMETALLICS; REDUCTION; SUBSTRATES;

CHLORIDE ELIMINATION; COBALOXIME;

OLEFINS;

EID: 33947664458     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om070027s     Document Type: Article

References (77)

1. (a) Schrauzer, G. N. Acc. Chem. Res. 1968, 1, 97-103.
2. (b) Bresciani-Pahor, N.; Forcolin, M.; Marzilli, L. G.; Randaccio, L.; Summers, M. F.; Toscano, P. J. Coord. Chem. Rev. 1985, 63, 1-125.
3. For some recent examples, see: (a) Gupta, B. D.; Yamuna, R.; Mandai, D. Organometallics 2006, 25, 706-7014.
4. (b) Mandai, D.; Gupta, D. B. Eur. J. Inorg. Chem. 2006, 4086-4095.
5. (c) Siega, P.; Randaccio, L.; Marzilli, P. A.; Marzilli, L. G. Inorg. Chem. 2006, 45, 3359-3368.
6. (d) Pidaparthi, R. R.; Welker, M. E.; Day, C. S. Organometallics 2006, 25, 974-981.
7. Fritsch, J. M.; Retka, N. D.; McNeill, K. Inorg. Chem. 2006, 45, 2288-2295.
8. (a) Hu, X.; Cossairt, B. M.; Brunschwig, B. S.; Lewis, N. S.; Peters, J. C. Chem. Commun. 2005, 4723-4725.
9. (b) Razavet, M.; Artero, V.; Fontecave, M. Inorg. Chem. 2005, 44, 4786-4795.
10. (a) Rich, A. E.; DeGreeff, A. D.; McNeill, K. Chem. Commun. 2002, 234-235.
11. (b) McKauley, K. M.; Wilson, S. R.; van der Donk, W. A. Inorg. Chem. 2002, 41, 393-404.
12. Gantzer, C. J.; Wackett, L. P. Environ. Sci. Technol. 1991, 25, 715-722.
13. Brown, K. L. Chem. Rev. 2005, 105, 2075-2149.
14. (a) Lesage, S.; Brown, S.; Millar, K. Environ. Sci. Technol. 1998, 32, 2264-2272.
15. (b) Glod, G.; Angst, W.; Hollinger, C.; Schwarzenbach, R. P. Environ. Sci. Technol. 1997, 31, 253-260.
16. (c) Glod, G.; Brodmann, U.; Angst, W.; Hollinger, C.; Schwarzenbach, R. P. Environ. Sci. Technol. 1997, 31, 3154-3160.
17. Costentin, C.; Robert, M.; Savéant, J.-M. J. Am. Chem. Soc. 2005, 127, 12154-12155.
18. Burris, D. R.; Delcomyn, C. A.; Smith, M. H.; Roberts, A. L. Environ. Sci. Technol. 1996, 30, 3047-3052.
19. For analogous dechlorination of alkyl halides, see, for example: Argüello, J. E.; Costentin, C.; Griveau, S.; Saveant, J.-M. J. Am. Chem. Soc. 2005, 127, 5049-5055, and references therein.
20. Fritsch, J. M.; McNeill, K. Inorg. Chem. 2005, 44, 4852-4861.
21. Follett, A. D.; McNeill, K. J. Am. Chem. Soc. 2005, 127, 844-845.
22. Pratt, D. A.; van der Donk, W. A. Chem. Commun. 2006, 558-560.
23. Liptak, M. D.; Brunold, T. C. J. Am. Chem. Soc. 2006, 128, 9144-9156.
24. (a) McKauley, K. M.; Wilson, S. R.; van der Donk, W. A. J. Am. Chem. Soc. 2003, 125, 4410-4411.
25. (b) McKauley, K. M.; Pratt, D. A.; Wilson, S. R.; Shey, J.; Burkey, T. J.; van der Donk, W. A. J. Am. Chem. Soc. 2005, 127, 1126-1136.
26. Nonnenberg, C.; van der Donk, W. A.; Zipse, H. J. Phys. Chem. A 2002, 106, 8708-8715.
27. Pratt, D. A.; van der Donk, W. A. J. Am. Chem. Soc. 2005, 127, 384-396.
28. Becke, A. D. Phys. Rev. A 1988, 38, 3098-3100.
29. (a) Perdew, J. P. Phys. Rev. B 1986, 33, 8822-8824.
30. (b) Perdew, J. P. Phys. Rev. B 1986, 34, 7406.
31. (a) Wachters, A. J. H. J. Chem. Phys. 1970, 52, 1033-1036.
32. (b) Hay, P. J. J. Chem. Phys. 1977, 66, 4377-4384.
33. (a) Hehre, W. J.; Ditchfield, R.; Pople, J. A. J. Chem. Phys. 1972, 56, 2257-2261.
34. (b) Hariharan, P. C.; Pople, J. A. Theor. Chim. Acta 1973, 28, 213-222.
35. Generated automatically according to the procedure implemented in Gaussian 03.
36. See for instance: Koch, W.; Holthausen, M. C. A Chemist's Guide to Density Functional Theory; Wiley-VCH: Weinheim, 2000.
37. In particular as far as geometries of transition-metal complexes are concerned, the popular B3LYP functional need not be superior to pure, gradient-corrected variants such as BP86; see for instance: (a) Hamprecht, F. A. H.; Cohen, A. J.; Tozer, D. J.; Handy, N. C. J. Chem. Phys. 1998, 109, 6264-6271.
38. (b) Barden, C. J.; Rienstra-Kiracofe, J. C.; Schaefer, H. F. J. Chem. Phys. 2000, 113, 690-700.
39. (c) Bühl, M.; Kabrede, H. J. Chem. Theor. Comput., in press.
40. (a) Krishnan, R.; Binkley, J. S.; Seeger, R.; Pople, J. A. J. Chem. Phys. 1980, 72, 650-654.
41. (b) Clark, T.; Chandrasekhar, J.; Spitznagel, G. W.; Schleyer, P. v. R. J. Comput. Chem. 1983, 4, 294-301.
42. As implemented in G 03: (a) Barone, V.; Cossi, M.; Tomasi, J. J. Comput. Chem. 1998, 19, 404-417.
43. (b) Cossi, M.; Scalmani, G.; Rega, N.; Barone, V. J. Chem. Phys. 2002, 117, 43-54.
44. (c) Cossi, M.; Crescenzi, O. J. Chem. Phys. 2003, 19, 8863-8872.
45. Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5642.
46. Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785-789.
47. Reed, A. E.; Curtiss, L. A.; Weinhold, F. Chem. Rev. 1988, 88, 899-926.
48. For a review on theoretical computations of electron affinities see: Rinstra-Kiracofe, J. C.; Tschumper, G. S.; Schaefer, H. F., III. Chem. Rev. 2002, 102, 231-282.
49. Lewis, A.; Bumpus, J. A.; Truhlar, D. G.; Cramer, C. J. J. Chem. Educ. 2004, 81, 596-604.
50. Winget, P.; Cramer, C. J.; Truhlar, D. G. Theor. Chem. Acc. 2004, 112, 217-227.
51. Frisch, M. J.; et al. Gaussian 03; Gaussian, Inc.: Pittsburgh, PA, 2003.
52. Bresciani-Pahor, N.; Randaccio, L.; Zangrando, E.; Toscano, P. J. Inorg. Chim. Acta 1985, 96, 193-198.
53. Patthabi, V.; Nethaji, M.; Gabe, E. J.; Lee, F. L.; Le, Page, Y. Acta Crystallogr. Sect. C 1984, 40, 1155.
54. Rossi, M.: Glusker, J. P.; Randaccio, L.; Summers, M. F.; Toscano, P. J.: Marzilli, L. G. J. Am. Chem. Soc. 1985, 107, 1729-1738.
55. There is also recent evidence from CASSCF calculations that DFT overestimates the Co-C BDE in methylcobalamin models: (a) Spataru, T.; Birke, R. L. J. Phys. Chem. A 2006, 110, 8599-8604. On the other hand, the BP86 functional has recently been shown to perform quite well in that respect:
56. (b) Kuta, J.; Patchkovskii, S.; Zgierski, M. Z.; Kozlowski, P. J. Comput. Chem. 2006, 27, 1429-1437.
57. Martin, B. D.; Finke, R. G. J. Am. Chem. Soc. 1992, 114, 585-592.
58. Birke, R. L.; Huang, Q.; Spataru, T.; Gosser, T. K., Jr. J. Am. Chem. Soc. 2006, 128, 1922-1936. The entropic contribution inferred in that study, TDS = 13.6 ± 1.5 kcal/mol at 293 K, compares favorably to that computed for the process in eq 1, 14.0 kcal/mol (in contrast, much smaller entropic effects have been found in ref 38, TDS = 7 ± 2 kcal/mol at 293 K).
59. See for example: (a) Randaccio, L.; Furlan, M.; Geremia, S.; Šlouf, M.; Srnova, I.; Toffoli, D. Inorg. Chem. 2000, 39, 3403-3413.
60. (b) Randaccio, L.; Geremia, S.; Nardin, G.; Wuerges, J. Coord. Chem. Rev. 2006, 250, 1332-1350.
61. (a) -0.63 V for Ti(III) chloride at pH 8; -0.70 V for the complex with ascorbate, cf. ref 7. (b) For Ti(III) citrate, an upper limit of -0.80 V has been estimated, cf. ref 17 in: Guo, M; Sulc, F.; Ribbe, M. W.; Farmer, P. J.; Burgess, B. K. J. Am. Chem. Soc. 2002, 124, 12100-12101.
62. Lexa, D.; Saveant, J.-M. Acc. Chem. Res. 1983, 16, 235-243.
63. See for example: Crudden, C. M.; Allen, D. P. Coord. Chem. Rev. 2004, 248, 2247-2273, and references therein.
64. That it is a chloride anion that is leaving, rather than a Cl radical, is apparent from population analyses, according to which the leaving Cl bears a charge of ca. -0.4e (both from Mulliken and natural population analysis).
65. 3 group, affording 5.
66. .- could be regarded as a Co(IV) species, a quite unusual oxidation state. For a recent paper on oxidized cobaloximes containing Co(IV) see: Ohkubo, K.; Fukuzumi, S. J. Phys. Chem. A 2005, 109, 1105-1113.
67. -6 au and opt = loose keyword.
68. The corresponding four-coordinate cob(I)alamin has been termed supernucleophile, cf. ref 14.
69. 4)]: Klein, H.-F.; Witty, H.; Schubert, U. Chem. Commun. 1983, 231-232.
70. Follett, A. D.; McNeill, K. Inorg. Chem. 2006, 45, 2727-2732.
71. Li, J., Fisher, C. L.; Chen, J. L.; Bashford, D.; Noodleman, L. Inorg. Chem. 1996, 35, 4694-4702.
72. ΔE(gas) = -13.5 kcal/mol, similar to values for the gas-phase electron affinity that have been obtained in experiments and DFT and ab initio calculations: (a) Chen, E. C. M.; Wiley, J. R.; Batten, C. F.; Wentworth, W. E. J. Phys. Chem. 1994, 98, 88-94.
73. (b) Bylaska, E. J.; Dupuis, M.; Tratnyek, P. G. J. Phys. Chem. A 2005, 109, 5905-5916.
74. A somewhat more negative value, -1.98 V, has been derived empirically in ref 8.
75. For the computation of such barriers in electron-transfer processes see for example: (a) Rosso, K. M.; Rustad, J. R. J. Phys. Chem. A 2000, 104, 6718-6725.
76. (b) Rosso, K. M.; Dupuis, M. Theor. Chem. Acc. 2006, 116, 124-136.
77. -) were found (also at restricted-open-shell DFT levels, cf.: Bylaska, E. J.; Dupuis, M.; Tratnyek, P. G. J. Phys. Chem. A 2005, 109, 5905-5916). For these σ* states, the computed reduction potentials of TCE, cis-DCE, and VC are -1.36, -1.67, and -1.83 V, respectively. In all cases, outer-sphere reduction of these olefins would appear less favorable than the inner-sphere mechanisms (cf. ΔG values in Table 3).