On the limits of highest-occupied molecular orbital driven reactions: The frontier effective-for-reaction molecular orbital concept

Journal of Physical Chemistry A

Volumn 110, Issue 3, 2006, Pages 1031-1040

  Da Silva, Rodrigo R ^a   Ramalho, Teodorico C ^a   Santos, Joana M ^b   Figueroa Villar, J Daniel ^a  

^a MILITARY INSTITUTE OF ENGINEERING   (Brazil)

^b STATE UNIVERSITY OF RIO DE JANEIRO   (Brazil)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOL FUELS; CARBOXYLIC ACIDS; CHEMICAL REACTIONS; CORRELATION METHODS; PHENOLS; SOLVENTS;

CONJUGATED BASES; DENSITY FUNCTIONAL; FERMOS; MOLECULAR ORBITAL DRIVEN REACTIONS;

ELECTRON ENERGY LEVELS;

EID: 84962381596     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp054434y     Document Type: Article

References (93)

1. Hehre, W. J.; Random, L.; Schleyer, P. v. R.; Pople, J. A. Ab Initio Molecular Orbital Theory, John Wiley & Sons: New York, 1986.
2. Jorgensen, W. L.; Briggs, J. M. J. Am. Chem. Sot: 1989, 111, 4190-4197.
3. Lim, C.; Bashford, D.; Karplus, M. J. Phys. Chem. 1991, 95, 5610-5620.
4. Chen, J. L.; Noodleman, L.; Case, D. A.: Bashford, D. J. Phys. Chem. 1994, 98, 11059-11068.
5. Li, G. S.; Ruiz-López, M. F.; Maigret, B. J. Phys. Chem. A 1997, 101, 7885-7892.
6. Schüürmann, G.; Cossi, M.; Barone, V.; Tomasi, J. J. Phys. Chem. A 1998, 102, 6706-6712.
7. Silva, C. O.; Silva, E. C.; Nascimento, M. A. C. J. Phys. Chem. A 1999, 103, 11194-11199.
8. Silva, C. O.; Silva, E. C.; Nascimento, M. A. C. J. Phys. Chem. A 2000, 104, 2404-2409.
9. Liptak, M. D.; Shields, G. C. J. Am. Chem. Soc. 2001, 123, 7314-7319.
10. Toth, A. M.; Liptak, M. D.; Phillips, D. L.; Shields, G. C. J. Chem. Phys. 2001, 114, 4595-4606.
11. Liptak, M. D.; Gross, K. C.; Seybold, P. G.; Feldgus, S.; Shields, G. C. J. Am. Chem. Soc. 2002, 124, 6421-6427.
12. Chipman, D. M. J. Phys. Chem. A 2002, 106, 7413-7422.
13. Adam, K. R. J. Phys. Chem. A 2002, 106, 11963-11972.
14. Klamt, A.; Eckert, F.; Diedenhofen, M.; Beck, M. E. J. Phys. Chem. A 2003, 107, 9380-9386.
15. Pytela, O.; Otyepka, M.; Kulhánek, J.; Otyepková, E.; Nevecná, T. J. Phys. Chem. A 2003, 107, 11489-11496.
16. Namazian, M.; Heidary, H. THEOCHEM 2003, 620, 257-263.
17. Chaudry, U. A.; Popelier, P. L. A. J. Org. Chem. 2004, 69, 233-241.
18. Fu, Y.; Liu, L.; Li, R.; Liu, R.; Guo, Q. J. Am. Chem. Soc. 2004, 126, 814-822.
19. Brinck, T.; Murray, J. S.; Politzer, P. J. Org. Chem. 1991, 56, 5012-5015.
20. Gross, K. C.; Seybold, P. G.; Peralta-Inga, Z.; Murray, J. S.; Politzer, P. J. Org. Chem. 2001, 66, 6919-6925.
21. Ma, Y.; Gross, K. C.; Hollingsworth, C. A.; Seybold, P. G.; Murray, J. S. J. Mol. Model. 2004, 10, 235-239.
22. Gross, K. C.; Seybold, P. G. Int. J. Quantum Chem. 2000, 80, 1107-1115.
23. Gross, K. C.; Seybold, P. G. Int. J. Quantum Chem. 2001, 85, 569-579.
24. Hollingsworth, C. A.; Seybold, P. G.; Hadad, C. M. Int. J. Quantum Chem. 2002, 90, 1396-1403.
25. Gruber, C.; Buss, V. Chemosphere 1989, 19, 15-95.
26. Machado, H. J. S.; Hinchliffe, A. THEOCHEM 1995, 339, 255-258.
27. Citra, M. J. Chemosphere 1999, 38, 191-206.
28. Soriano, E.; Cerdán, S.; Ballesteros, P. THEOCHEM 2004, 684, 121-128.
29. Fujimoto, H.; Mizutani, Y.; Iwaze, K. J. Phys. Chem. 1986, 90, 2768-2772.
30. Fujimoto, H. Acc. Chem. Res. 1987, 20, 448-453.
31. Omoto, K.; Fujimoto, H. J. Am. Chem. Soc. 1997, 119, 5366-5372.
32. Hirao, H.; Ohwada, T. J. Phys. Chem. A 2003, 107, 2875-2881.
33. Nakamura, S.; Hirao, H.; Ohwada, T. J. Org. Chem. 2004, 69, 4309-4316.
34. Ohwada, T.; Hirao, H.: Ogawa, A. J. Org. Chem. 2004, 69, 7486-7494.
35. Hirao, H.; Ohwada, T. J. Phys. Chem. A 2005, 109, 816-824.
36. Szabo, A.; Ostlund, N. S. Modern Quantum Chemistry. Introduction to Advanced Electronic Structure Theory; McGraw-Hill Publishing Company: New York, 1989.
37. Itatani, J.; Levesque, J.; Zeidler, D.; Niikura, H.; Pépin, H.; Kieffer, J. C.; Corkum, P. B.; Villeneuve, D. M. Nature 2004, 432, 867-871.
38. Koopmans, T. A. Physica 1933, 1, 104-113.
39. Fukui, K.; Yonezawa, T., Shingu, H. J. Chem. Phys. 1952, 20, 722-725.
40. Fukui, K.; Yonezawa, T.; Nagata, C.; Shingu, H. J. Chem. Phys. 1954, 22, 1433-1442.
41. Woodward, R. B.; Hoffmann, R. J. Am. Chem. Soc. 1965, 87, 395-397.
42. Hoffmann, R.; Woodward, R. B. J. Am. Chem. Soc. 1965, 87, 2046-2048.
43. Woodward, R. B.; Hoffmann, R. J. Am. Chem. Soc. 1965, 87, 2511-2513.
44. Hoffmann, R.; Woodward, R. B. J. Am. Chem. Soc. 1965, 87, 4388-4389.
45. Hoffmann, R.; Woodward, R. B. J. Am. Chem. Soc. 1965, 87, 4389-4390.
46. Hoffmann, R.; Woodward, R. B. Acc. Chem. Res. 1968, 1, 17-22.
47. Woodward, R. B.; Hoffmann, R. Angew. Chem. 1969, 81, 797-870.
48. Salem, L. J. Am. Chem. Soc. 1968, 90, 543-552.
49. Salem, L. J. Am. Chem. Soc. 1968, 90, 553-566.
50. Houk, K. N. Acc. Chem. Res. 1975, 11, 361-369.
51. Fujimoto, H.; Sugiyama, T. J. Am. Chem. Soc. 1977, 99, 15-22.
52. Fujimoto, H.; Inagaki, S.; J. Am. Chem. Soc. 1977, 99, 7424-7432.
53. Pearson, R. G. J. Am. Chem. Soc. 1963, 55, 3533-3539.
54. Klopman, G. J. Am. Chem. Soc. 1968, 90, 223-234.
55. Pearson, R. G. J. Am. Chem. Soc. 1986, 108, 6109-6114.
56. Hohenberg, P.; Kohn, W. Phys. Rev. 1964, 136, B864-B871.
57. Kohn, W.; Sham, L. J. Phys. Rev. 1965. 140, A1133-A1138.
58. Kohn, W.; Becke, A. D.; Parr, R. G.; J. Phys. Chem. 1996, 100, 12974-12980.
59. Politzer, P.; Abu-Awwad, F. Theor, Chem. Acc. 1998, 99, 83-87.
60. Baerends, E. J.; Gritsenko, O. V. J. Phys. Chem. 1997, 101, 5383-5403.
61. Politzer, P.; Abu-Awaad, F.; Murray, J. S.; Int. J. Quantum Chem. 1998, 69, 607-613.
62. Brunold, T. C.; Gamelin, D. R.; Solomon, E. I. J. Am. Chem. Soc. 2000, 122, 8511-8523.
63. Chen, P.; Fujisawa, K.; Solomon, E. I. J. Am. Chem. Soc. 2000, 122, 10177-10193.
64. Randall, D. W.; George, S. D.; Hedman, B.; Hodgson, K. O.; Fujisawa, K.; Solomon, E. I. J. Am. Chem. Soc. 2000, 122, 11620-11631.
65. Randall, D. W.; George, S. D.; Holland, P. L.; Hedman, B.; Hodgson, K. O.; Tolman, W. B.; Solomon, E. I. J. Am. Chem. Soc. 2000, 122, 11632-11648.
66. Cheng, P.; Solomon, E. I. J. Inorg. Biochem. 2002, 88, 368-374.
67. Skulan, A. J.; Hanson, M. A.; Hsu, H.; Dong, Y.; Que, L., Jr.: Solomon, E. I. Inorg. Chem. 2003, 42, 6489-6496.
68. Schenk, G.; Pau, M. Y. M.; Solomon, E. I. J. Am. Chem. Soc. 2004, 126, 505-515.
69. Basumallick, L.; Sarangi, R.; George, S. D.; Elmore, B.; Hooper, A. B.; Hedman, B.; Hodgson, K. O.; Solomon, E. I. J. Am. Chem. Soc. 2005, 127, 3531-3544.
70. Savin, A.; Umrigar, C. J.; Gonze, X. Chem. Phys. Lett. 1998, 288, 391-395.
71. Stowasser, R.; Hoffmann, R. J. Am. Chem. Soc. 1999, 121, 3414-3420.
72. Frisch, M. J., et al. Gaussian 98, revision A.11; Gaussian, Inc.: Pittsburgh, PA, 2001.
73. Becke, A. D. J. Chem. Phvs. 1993, 98, 5648-5652.
74. Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785-789.
75. Miertuš, S.: Scrocco, E.; Tomasi, J. Chem. Phys. 1981, 55, 117-129.
76. Miertuš, S.; Tomasi, J. Chem. Phys. 1982, 65, 239-245.
77. Cossi, M.; Barone, V.; Cammi, R.; Tomasi, J. Chem. Phys. Lett. 1996, 255, 327-335.
78. Klamt, A.; Schüürmann, G. J. Chem. Soc., Perkins Trans. 1993, 2, 799 -805.
79. Barone, V.; Cossi, M. J. Phys. Chem. A 1998, 102, 1995-2001.
80. We are using the orbital shapes instead of orbital symmetries for two main reasons. First, since we did not constrain the symmetry in the calculations, all but few molecules belong to Cl group and the orbital symmetries are na, where n is the orbital number. Second, the orbital symmetry group does not help us find the orbital location in a molecule (although in other cases the symmetry does). Thus, we must check their shapes to have this information. In this particular case, the orbital shape gives more useful information than symmetry does.
81. Skoog, D. A.; West, D. M.; Holler, F. J. Analytical Chemistry. An Introduction; Saunders College Publishing: 1994.
82. See Supporting Information for complete results.
83. Box, G. E. P.; Hunter, W. G.; Hunter, J. S. Statistics for Experiments. An Introduction to Design, Data Analysis, and Model Building; John Wiley & Sons: 1978.
84. z ones by the remaining p atomic orbital.
85. We thank the reviewers for this discussion.
86. Edward, J. T. J. Chem. Educ. 1982, 59, 354-356.
87. Compound 35 has a difference between the regression and calculated MO energy higher than four times the standard deviation.
88. Exner, O.; Böhm, S. J. Org. Chem. 2002, 67, 6320-6327.
89. Exner, O.;_ársky, P. J. Am. Chem. Soc. 2001, 123, 9564-9570.
90. Fukui, K. Angew. Chem., Int. Ed. Engl. 1982, 27, 801-809.
91. If the molecule is too small, it is possible that only one MO could drive different reactions.
92. Murali, R.; Scheeren, H. W. Tetrahedron Lett. 1999, 40, 3029-3032.
93. Hirao, H.; Ohwada, T. J. Phys. Chem. A 2005, 109, 7642-7647.