Mechanistic insights into NO 3 ̇ induced self-terminating radical oxygenations, part 1: A computational study on NO 3 ̇ and its addition to alkynes

Journal of Physical Chemistry A

Volumn 110, Issue 6, 2006, Pages 2195-2203

  Wille, Uta ^a,b   Dreessen, Tim ^a,c,d  

^a UNIVERSITY OF MELBOURNE   (Australia)

^b UNIVERSITY OF MELBOURNE   (Australia)

^c UNIVERSITY OF KIEL   (Germany)

^d Otto Diels Institut für Organische Chemie   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

HARTREE-FOCK (HF); HYBRID DENSITY FUNCTIONALS; METHYL GROUP;

CHEMICAL BONDS; DATA ACQUISITION; GROUND STATE; PROBABILITY DENSITY FUNCTION;

NITROGEN OXIDES;

EID: 33644783053     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp0454772     Document Type: Article

References (88)

1. See for example: Wayne, R. P.; Barnes, I.; Biggs, P.; Burrows, J. P.; Canosa-Mas, C. E.; Hjorth, J.; Le Bras, G.; Moortgat, G. K.; Perner, D.; Restelli, G.; Sidebottom, H. The Nitrate Radical: Physics, Chemistry and the Atmosphere. Atmos. Environ. 1991, A25; and cited references.
2. (a) Wille, U.; Plath, C. Liebigs Ann./Recueil 1997, 111.
3. (b) Wille, U.; Lietzau, L. Tetrahedron 1999, 55, 10119.
4. (c) Wille, U.; Lietzau, L. Tetrahedron 1999, 55, 11465.
5. (d) Lietzau, L.; Wille, U. Heterocycles 2001, 55, 377.
6. (e) Wille, U. Chem.-Eur. J. 2002, 8, 340.
7. (f) Dreessen, T.; Jargstorff, C.; Lietzau, L.; Plath, C.; Stademann, A.; Wille, U. Molecules 2004, 9, 480.
8. (g) Stademann, A.; Wille, U. Aust. J. Chem. 2004, 57, 1055.
9. A mechanistic scheme for a typical self-terminating radical oxygenation is given in the electronic Supporting Information.
10. The calculations of the remaining reaction steps of the self-terminating radical oxygenation sequence will be presented separately: Dreessen, T.; Wille, U. Unpublished results.
11. (a) Olsen, J. F.; Burnelle, L. J. Am. Chem. Soc. 1970, 92, 3659.
12. (b) Baird, N. C.; Taylor, K. F. Chem. Phys. Lett. 1981, 80, 83.
13. (c) Kim, B.; Johnston, H. S.; Clabo, D. A., Jr.; Schaefer, H. F., III J. Chem. Phys. 1988, 88, 3204.
14. (d) Boehm, R. C.; Lohr, L. L. J. Phys. Chem. 1989, 93, 3430.
15. (e) Boehm, R. C.; Lohr, L. L. J. Comput. Chem. 1991, 12, 119.
16. (f) Davy, R. D.; Schaefer, H. F., III J. Chem. Phys. 1989, 91, 4410.
17. (g) Kim, B.; Hammond, B. L.; Lester, W. A., Jr.; Johnston, H. S. Chem. Phys. Lett. 1990, 168, 131.
18. (h) Morris, V. R.; Bhatia, S. C.; Hall, J. H., Jr. J. Phys. Chem. 1990, 94, 7414.
19. (i) Morris, V. R.; Bhatia, S. C.; Hall, J. H., Jr. J. Phys. Chem. 1991, 95, 9203.
20. (a) Kim, B.; Hunter, P. L.; Johnston, H. S. J. Chem. Phys. 1992, 96, 4057.
21. (b) Friedl, R. R.; Sander, S. P. J. Phys. Chem. 1987, 91, 2721.
22. (c) Ishiwata, T.; Tanaka, I.; Kawaguchi, K.; Hirota, E. J. Chem. Phys. 1985, 82, 2196.
23. (d) Kawaguchi, K.; Hirota, E.; Ishiwata, T.; Tanaka, I. J. Chem. Phys. 1990, 93, 951.
24. (e) Kawaguchi, K.; Ishiwata, T.; Tanaka, I.; Hirota, E. Chem. Phys. Lett. 1991, 180, 436.
25. (f) Kawaguchi, K.; Ishiwata, T.; Hirota, E.; Tanaka, I. Chem. Phys. 1998, 231, 193.
26. (g) Ishiwata, T.; Tanaka, I.; Kawaguchi, K.; Hirota, E. J. Mol. Spectrosc. 1992, 153, 167.
27. (h) Weaver, A.; Arnold, D. W.; Bradford, S. E.; Neumark, D. M. J. Chem. Phys. 1991, 94, 1740.
28. (i) Monks, P. S.; Stief, L. J.; Krauss, M.; Kuo, S. C.; Zhang, Z.; Klemm, R. B. J. Phys. Chem. 1994, 98, 10017.
29. (j) Wang, D.; Jiang, P.; Qian, X.; Hong, G. J. Chem. Phys. 1997, 106, 3003.
30. Symmetry breaking is an artifact caused by an inadequately approximated solution of the electronic Schrödinger equation and is frequently encountered in computations of highly symmetric open-shell molecules; see for example: (a) McLean, A. D.; Lengsfeld, B. H., III; Pacansky, J.; Ellinger, Y. J. Chem. Phys. 1985, 83, 3567.
31. (b) Sherill, C. D.; Lee, M. S.; Head-Gordon, M. Chem. Phys. Lett. 1999, 302, 425.
32. (c) Cohen, R. D.; Sherill, C. D. J. Chem. Phys. 2001, 114, 8257.
33. Eisfeld, W.; Morokuma, K. J. Chem. Phys. 2000, 113, 5587.
34. (a) Stirling, A.; Pápai, I.; Mink, J.; Salahub, D. R. J. Chem. Phys. 1994, 100, 2910.
35. (b) Munakata, H.; Kakumoto, T.; Baker, J. THEOCHEM 1997, 391, 231.
36. (c) Aplincourt, P.; Bohr, F.; Ruiz-Lopez, M. F. THEOCHEM 1998, 426, 95.
37. Slater, J. C. Quantum Theory of Molecular and Solids. Vol. 4: The Self-Consistent Field for Molecular and Solids; McGraw-Hill: New York, 1974.
38. Vosko, S. H.; Wilk, L.; Nusair, M. Can. J. Phys. 1980, 58, 1200.
39. Becke, A. D. Phys. Rev. A 1988, 38, 3098.
40. Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.
41. Perdew, J. P. Phys. Rev. B 1986, 33, 8822.
42. Perdew, J. P.; Wang, Y. Phys. Rev. B 1992, 45, 13244.
43. Davis, H. F.; Kim, B.; Johnston, H. S.; Lee, Y. T. J. Phys. Chem. 1993, 97, 2172.
44. Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
45. Truong, T. N.; Duncan, W. J. Chem. Phys. 1994, 101, 7408.
46. Frisch, A.; Frisch, M. J. Gaussian 98 Users Reference; Gaussian Inc.: Pittsburgh, PA, 1998.
47. (a) Perdew, J. P. In Electronic Structure of Solids'91; Ziesche, P., Eschrig, H., Eds.; Akademie Verlag: Berlin, 1991.
48. (b) Perdew, J. P.; Chevary, J. A.; Vosko, S. H.; Jackson, K. A.; Pederson, M. E.; Singh, D. J.; Fiolhais, C. Phys. Rev. B 1992, 46, 6671.
49. (c) Perdew, J. P.; Chevary, J. A.; Vosko, S. H.; Jackson, K. A.; Pederson, M. R.; Singh, D. J.; Fiolhais, C. Phys. Rev. B 1993, 48, 4978.
50. (d) Burke, K.; Perdew, J. P.; Wang, Y. In Electronic Density Functional Theory: Recent Progress and New Directions; Dobson, J. F., Vignale, G., Das, M. P., Eds.; Plenum: New York, 1998.
51. (e) Perdew, J. P.; Burke, K.; Wang, Y. Phys. Rev. B 1996, 54, 16533.
52. (f) Adamo, C.; Barone, V. J. Chem. Phys. 1998, 108, 664.
53. The mPW1K functional was optimized for hydrogen abstraction reactions; see for example: Lynch, B. J.; Fast, P. L.; Harris, M.; Truhlar, D. G. J. Phys. Chem. A 2000, 104, 4811.
54. (a) Pérez-Casany, M. P.; Nebot-Gil, I.; Sánchez-Martin, J.; Thomás-Vert, F.; Martínez-Ataz, E.; Cabañas-Galán, B.; Aranda-Rubio, A. J. Org. Chem. 1999, 63, 6987.
55. (b) Cartas-Rosado, R.; Santoyo, M. E. R.; Alvarez-Idaboy, J. R.; Vivier-Bunge, A. J. Phys. Chem. A 2001, 105, 9222.
56. (c) Pérez-Casany, M. P.; Nebot-Gil, I.; Sánchez-Martin, J. J. Phys. Chem. A 2000, 104, 6277.
57. (d) Pérez-Casany, M. P.; Nebot-Gil, I.; Sánchez-Martin, J. J. Phys. Chem. A 2000, 104, 10721.
58. (e) Pérez-Casany, M. P.; Nebot-Gil, I.; Sánchez-Martin, J. J. Phys. Chem. A 2000, 104, 11340.
59. (f) Pérez-Casany, M. P.; Sánchez-Martin, J.; Nebot-Gil, I. J. Am. Chem. Soc. 2000, 122, 11585.
60. (a) Atkinson, R. J. Phys. Chem. Ref. Data 1991, 20, 459.
61. (b) Canosa-Mas, C. E.; Smith, S. J.; Toby, S.; Wayne, R. P. J. Chem. Soc., Faraday Trans. 2 1988, 84, 247.
62. (c) Canosa-Mas, C. E.; Smith, S. J.; Toby, S.; Wayne, R. P. J. Chem. Soc., Faraday Trans. 2 1988, 84, 263.
63. (d) Benter, T.; Becker, E.; Wille, U.; Schindler, R. N.; Canosa-Mas, C. E.; Smith, S. J.; Waygood, S. J.; Wayne, R. P. J. Chem. Soc., Faraday Trans. 2 1991, 87, 2141.
64. (e) Seland, J. G.; Noremsaune, I. M. W.; Nielsen, C. J. J. Chem. Soc., Faraday Trans. 1996, 92, 3459.
65. (f) Atkinson, R.; Aschmann, S. M.; Goodman, M. A. Int. J. Chem. Kinet. 1987, 19, 299.
66. (a) 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.11.4; Gaussian, Inc.: Pittsburgh, PA, 2002.
67. (b) 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.7; Gaussian, Inc.: Pittsburgh, PA, 1998.
68. (c) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T.; Petersson, G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Cioslowski, J.; Stefanov, B. B.; Nanayakkara, A.; Challacombe, M.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J. L.; Replogle, E. S.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.; Defrees, D. J.; Baker, J.; Stewart, J. P.; Head-Gordon, M.; Gonzalez, C.; Pople, J. A. Gaussian 94, revision D.4/E.2; Gaussian, Inc.: Pittsburgh, PA, 1995.
69. This energy difference is lesser than the precision that normally is assigned to the theoretical methods.
70. Crawford, T. D.; Stanton, J. F. J. Chem. Phys. 2000, 112, 7873.
71. Janoschek, R.; Kalcher, J. Z. Anorg. Allg. Chem. 2002, 628, 2724.
72. In our computations, basis sets with diffuse functions generally resulted in higher absolute values for the atomic charges and dipole moments (see Supporting Information).
73. o was determined according to: Ochterski, J. W. http://www.gaussian.com/g_whitepap/thermo.htm (Accessed 2000).
74. -1, they were not further considered.
75. Since this supermolecule is not symmetric at all, no symmetry breaking problems should appear.
76. Curran, D. P.; Porter, N. A.; Giese, B. Stereochemistry of Radical Reactions; VCH: Weinheim, 1996.
77. No attempt was made in this work to locate the transition state of the Z/E isomerization of the vinyl radicals because of the expected low activation barrier and its insignificance for the course of the radical oxygenation cascade; see also: Fossey, J.; Lefort, D.; Sorba, J. Free Radicals in Organic Chemistry; John Wiley & Sons: Chichester, 1995.
78. ̇ to alkynes to benchmark our computational results. The rates of these reactions are on the lower limit accessible by the fast-flow techniques that were used for their determination, and the obtained data are consequently afflicted with significant errors; see refs 1 and 23a-d.
79. The B3LYP method is well-known to underestimate the size of activation barriers in radical reactions; see ref 22b.
80. ̇ attack at the higher substituted site of the C≡C triple bond was not investigated; see ref 22c and:
81. (a) Vereecken, L.; Peeters, J.; Bettinger, H. F.; Kaiser, R. I., Schleyer, P. v. R.; Schaefer, H. F., III J. Am. Chem. Soc. 2002, 124, 2781.
82. (b) Fischer, H.; Radom, L. Angew. Chem., Int Ed. 2001, 40, 1340.
83. NOC1C2 of ca. 180° were located as transition states of the rotation between the two enantiomers of E-p and Z-p, respectively (not shown).
84. ̇ with ethyne.
85. 1.
86. Lee, T. J.; Head-Gordon, M.; Rendell, A. P. Chem. Phys. Lett. 1995, 243, 402.
87. This might be because DFT methods cannot reproduce intermolecular interactions well. The calculated geometries for complex-e/p/b showed indeed the largest dependencies on the theoretical level of theory used in this work (see Supporting Information).
88. Similar to our results, it was found that addition of methyl and phenyl radicals to ethyne or propyne leads, via Z-configurated transition states, to Z-configurated vinyl radicals; see refs 36a and: Gómez-Balderas, R.; Coote, M. L.; Henry, D. J.; Fischer, H.; Radom, L. J. Phys. Chem. A 2003, 107, 6082.