Effective Way of Modeling Chemical Catalysis: Empirical Valence Bond Picture of Role of Solvent and Catalyst in Alkylation Reactions

Journal of Computational Chemistry

Volumn 21, Issue 8, 2000, Pages 607-625

  Villà, Jordi ^a,b,c   Bentzien, Jörg ^b,d   González Lafont, Angels ^a   Lluch, José M ^a   Bertran, Juan ^a   Warshel, Arieh ^b  

^a UNIVERSITAT AUTÒNOMA DE BARCELONA   (Spain)

^b UNIVERSITY OF SOUTHERN CALIFORNIA   (United States)

^c INST MUNIC D INVESTIGACIO MEDICA   (Spain)

^d Xencor Inc   (United States)

Author keywords

Alkylation reactions; Chemical catalysis; Complex reactions; Empirical valence bond (EVB); Langevin dipoles (LD)

Indexed keywords

EID: 84962408954     PISSN: 01928651     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1096-987X(200006)21:8<607::AID-JCC3>3.0.CO;2-R     Document Type: Article

References (90)

1. (a) Friedel, C.; Crafts, J. M. Comput Rend 1877, 84, 1450;
2. (b) Friedel, C.; Crafts, J. M. Comput Rend 1877, 85, 74.
3. Olah, G. A. In: Olah, G. A., Ed. Friedel-Crafts and Related Reactions, Vol. I; Wiley: New York, 1963; p. 25.
4. Olah, G. A.; Pavlath, A.; Olah, J. J Chem Soc 1957, 2174.
5. Drahowzal, F. A. In: Olah, G. A., Ed., Friedel-Crafts and Related Reactions, Vol. II; Wiley: New York, 1964; p. 417.
6. Olah, G. A. In: Olah, G. A., Ed. Friedel-Crafts and Related Reactions, Vol. I; Wiley: New York, 1963; p. 201.
7. Bazz, M.; Gutmann, V. In: Olah, G. A., Ed., Friedel-Crafts and Related Reactions, Vol. I; Wiley: New York, 1963; p. 367.
8. (a) Jenny, R. Comput Rend 1958, 246, 3477;
9. (b) Jenny, R. Comput Rend 1959, 248, 3555;
10. (c) Jenny, R. Comput Rend 1960, 250, 1659.
11. (a) Nakana, R.; Oyana, T. J Phys Chem 1966, 70, 1146;
12. (b) Nelson, H. M. J Phys Chem 1962, 66, 1380;
13. (c) Olah, G. A.; DeMember, R. H.; Schlosberg, R. H. J Am Chem Soc 1970, 92, 2562;
14. (d) Olah, G. A.; DeMember, J. H.; Schlosberg, R. H.; Halpem, Y. J Am Chem Soc 1972, 94, 156;
15. (e) Olah, G. A.; Meyer, M. M. In: Olah, G. A., Ed., Friedel-Crafts and Related Reactions, Vol. I; Wiley: New York, 1963; p. 623.
16. Olah, G. A.; Prakash, G. K. S.; Williams, R. E.; Field, L. D.; Wade, K. In: Hydrocarbon Chemistry; Wiley: New York, 1987.
17. (a) Brown, H. C.; Grayson, M. J Am Chem Soc 1953, 75, 6285;
18. (b) Jungk, H.; Smoot, C. R.; Brown, H. C. J Am Chem Soc 1956, 78, 2185;
19. (c) Brown, H. C.; Belta, B. A. J Am Chem Soc 1959, 81, 3520.
20. (a) Olah, G. A.; Klopman, G.; Schosberg, H. J Am Chem Soc 1969, 91, 3261;
21. (b) Olah, G. A. Angew Chem Int Ed 1973, 12, 173.
22. (a) Epiotis, N. D.; Larson, J. R.; Eaton, H. In: Unified Valence Bond Theory of Electronic Structure; Springer: Heidelberg, 1982;
23. (b) Shaik, S. S.; Pross, A. J Am Chem Soc 1982, 104, 2708;
24. (c) Pross, A.; Shaik, S. S. Acc Chem Res 1983, 16, 363;
25. (d) Shaik, S. S. Prog Phys Org Chem 1985, 15, 197.
26. (a) Bernardi, F.; Robb, M. A. Adv Chem Phys 1987, 67, 155;
27. (b) Bernardi, F.; McDowall, J. J. W.; Robb, M. A. J Comput Chem 1987, 8, 296;
28. (c) Bernardi, F.; Robb, M. A. J Am Chem Soc 1984, 106, 54;
29. (d) Bernardi, F.; Olivucci, M.; Robb, M. A. Acc Chem Rev 1990, 23, 405.
30. (a) Warshel, A. In: Computer Modeling of Chemical Reactions in Enzymes and in Solutions; Wiley: New York, 1991;
31. (b) Warshel, A.; Weiss, R. M. J Am Chem Soc 1980, 102, 6218;
32. (c) Warshel, A.; Sussman, F.; Hwang, J. K. J Mol Biol 1988, 201, 139;
33. (d) Hwang, J. K.; King, G.; Creighton, S.; Warshel, A. J Am Chem Soc 1988, 110, 5297;
34. (e) Åqvist, J.; Warshel, A. Biochemistry 1988, 28, 4680;
35. (f) Åqvist, J.; Warshel, A. Chem Rev 1993, 93, 2523;
36. (g) Lee, F. S.; Chu, Z. T.; Warshel, A. J Comput Chem 1993, 14, 161.
37. (a) Kim, H. J.; Hynes, J. T. Int J Quantum Chem Quantum Chem Symp 1990, 24, 821;
38. (b) Kim, H. J.; Hynes, J. T. J Am Chem Soc 1992, 114, 10508;
39. Kim, H. J.; Hynes, J. T. J Am Chem Soc 1992, 114, 10528;
40. (d) Chang, Y.-T; Miller, W. H. J Phys Chem 1990, 94, 5884;
41. (e) Chang, Y.-T.; Minichino, C.; Miller, W. H. J Chem Phys 1992, 96, 4341;
42. (f) Bala, P.; Grochowski, P.; Lesyng, B.; McCammon, J. A. In: Bicout, D.; Field, M., Eds., Quantum Mechanical Simulation Methods for Studying Biological Systems; Springer: Berlin, 1995; p. 119;
43. (g) Grochowski, P.; Lesyng, B.; Bala, P.; McCammon, J. A. Int J Quantum Chem 1996, 60, 1143;
44. (h) Bala, P.; Grochowski, P.; Lesyng, B.; McCammon, J. A. J Phys Chem 1996, 100, 2535;
45. (i) Lobaugh, J.; Voth, G. A. J Chem Phys 1994, 100, 3039;
46. (j) Neria, E.; Karplus, M. 1997, 267, 23;
47. (k) Vuilleumier, R.; Borgis, D. Chem Phys Lett 1998, 284, 71;
48. (l) Schmitt, U. W.; Voth, G. A. J Phys Chem 1998, 102, 5547;
49. (m) Kim, Y.; Corchado, J. C.; Villa, J.; Xing, J.; Truhlar, D. G. J Chem Phys 2000, 112, 2718.
50. 15h that a new microscopic model (called AVB) had been developed. This argument was based on the assertion that the EVB model is calibrated on macroscopic thermodynamic data while the so-called AVB approach is calibrated on ab initio gas-phase results. This argument reflects a very problematic perspective. First, the EVB model provides fully microscopic all-atom molecular surfaces that are always calibrated on the most reliable information available at the given time. This, of course, includes ab initio results when these results are considered to be sufficiently reliable (e.g., refs. 14d, 15d, and 15i). Second, the argument that calibration of a microscopic model using macroscopic properties makes the model macroscopic is simply misleading. As is now obvious to almost all workers in the field one of the best ways of calibrating microscopic models is the use of these models in simulations of average properties (e.g., solvation free energies) and then using the agreement between the calculated and observed properties in refining the microscopic level. This is, for example, the approach used in refining popular water models and many force fields. Finally, as a note of caution, even now, with very powerful ab initio approaches, it is important to verify the calculated results using experimental information about the given reaction in solution. This is demonstrated in the present work and not doing so will lead to incorrect results in calculations of complex systems such as enzymatic reactions.
51. Wesolowski, T.; Warshel, A. J Phys Chem 1994, 98, 5183.
52. Branchadell, V.; Oliva, A.; Bertrán, J. J Chem Soc Perkin Trans II 1989, 1091.
53. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T. A.; Petersson, G. A.; Montgomery, J. A.; Raghavachari, K.; AlLaham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Ciolowski, 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; Gaussian: Pittsburgh, PA, 1995.
54. Florián, J.; Warshel, A. J Phys Chem 1997, 101, 5583.
55. (a) Florián, J.; Warshel, A. CHEMSOL, version 1.12; University of Southern California: Los Angeles, 1997;
56. (b) Program CHEMSOL can be downloaded from the anonymous ftp server usc.edu, directory /pub/warshel/cs.
57. Miertus, S.; Scrocco, E.; Tomasi, J. J Chem Phys 1981, 55, 117.
58. Kong, Y. S.; Warshel, A. J Am Chem Soc 1995, 117, 6234.
59. Muller, R. P.; Warshel, A. J Phys Chem 1995, 99, 17516.
60. (a) Chandrasekhar, J.; Smith, S. F.; Jorgensen, W. L. J Am Chem Soc 1985, 107, 154;
61. (b) Chandrasekhar, J.; Jorgensen, W. L. J Am Chem Soc 1985, 107, 2974.
62. Villà, J.; Warshel, A. SIMPLE VB, University of Southern California: Los Angeles, CA, 1999.
63. (a) Goldberg, D. E. In: Genetic Algorithms in Search, Optimization & Machine Learning; Addison-Wesley: Reading, MA, 1989;
64. (b) Carroll, D. L. GA, version 1.6.4, University of Illinois at Urbana-Champaign: Urbana, IL, 1997.
65. (a) Villà, J.; González-Lafont, A.; Lluch, J. M.; Truhlar, D. G. J Am Chem Soc 1998, 120, 5559;
66. (b) Villà, J.; Corchado, J. C.; González-Lafont, A.; Lluch, J. M.; Truhlar, D. G. J Am Chem Soc 1998, 120, 12141;
67. (c) Villà, J.; Corchado, J. C.; González-Lafont, A.; Lluch, J. M.; Truhlar, D. G. J Phys Chem A 1999, 103, 5061.
68. Hay, P. J.; Wadt, W. R. J Chem Phys 1985, 82, 299.
69. (a) Hwang, J.-K.; Warshel, A. J Am Chem Soc 1987, 109, 715;
70. (b) Lee, F. S.; Chu, Z. T.; Bolger, M. B.; Warshel, A. Prot Eng 1992, 5, 215.
71. Abraham, M. H. In: Bamford, C. H.; Tipper, C. F. H., Eds., Comprehensive Chemical Kinetics, Vol. 12; Elsevier: Amsterdam, 1973.
72. (a) Krishnan, R.; Binkley, J. S.; Seeger, R.; Pople, J. A. J Chem Phys 1980, 72, 650;
73. (b) Møller, C.; Plesset, M. S. Phys Rev 1934, 46, 618.
74. Warshel, A.; Hwang, J. K.; Åqvist, J. Faraday Discuss 1992, 93, 225.
75. (a) Yakobson, G. G.; Furin, G. G. Synthesis 1980, 345, and references therein;
76. (b) DeHaan, F. P.; Delker, G. L.; Covey, W. D.; Ahn, J.; Anisman, M. S.; Brehm, E. C.; Chang, J.; Chicz, R. M.; Cowan, R. L.; Ferrara, D. M.; Fong, C. H.; Harper, J. D.; Irani, C. D.; Kim, J. Y.; Meinhold, R. W.; Miller, K. D.; Roberts, M. P.; Stoler, E. M.; Suh, Y. J.; Tang, M.; Williams, E. C. J Am Chem Soc 1984, 106, 7038.
77. Kong, Y. S.; Warshel, A. J Am Chem Soc 1995, 117, 6234.
78. Tuñón, I.; Silla, E.; Bertrán, J. J Chem Soc Faraday Trans 1994, 90, 1757.
79. Dean, J. A. Lange's Handbook of Chemistry; McGraw-Hill: New York, 1992.
80. Pearson, R. G. J Am Chem Soc 1986, 108, 6109.
81. Lide, D. R., Ed. Handbook of Chemistry and Physics, 77th ed.; CRC Press: Boca Raton, FL, 1996.
82. Benson, S. W. In: Thermochemical Kinetics; Wiley: New York, 1976.
83. Frenkel, M.; Marsh, K. N.; Wilhoit, R. C.; Kabo, G. J.; Roganov, G. N. In: Thermodynamic of Organics Compounds in the Gas State, Vol. 1, TRC Data Series; Thermodynamic Research Center: College Station, TX, 1994.
84. Ben-Naim, A. In: Solvation Thermodynamics; Plenum Press: New York, 1987.
85. Alberty, R. A.; Gehrig, C. A. J Chem Phys Ref Data 1984, 13, 1173.
86. Alberty, R. A. J Chem Phys Ref Data 1985, 14, 177.
87. Lias, S. G.; Liebman, J. F.; Levin, R. D. J Phys Chem Ref Data 1984, 13, 695.
88. Kriemler, P.; Buttrill, S. E., Jr. J Am Chem Soc 1973, 95, 1365.
89. Chelkowski, A. In: Dielectric Physics; Elsevier: Amsterdam, 1980.
90. Meller, A. In: Gmelin Handbook of Inorganic Chemistry, Boron Compounds, Vol. 3, 3rd supplement; Springer: New York, 1988.