Understanding reactivity with Kohn-Sham molecular orbital theory: E2-SN2 mechanistic spectrum and other concepts

Journal of Computational Chemistry

Volumn 20, Issue 1, 1999, Pages 114-128

  Bickelhaupt, F Matthias ^a  

^a PHILIPPS UNIVERSITY MARBURG   (Germany)

Author keywords

Density functional theory; Elimination; Mechanistic concepts; Orbital interactions; Oxidative addition; Reaction mechanisms; Reactivity; Substitution

Indexed keywords

EID: 5244255090     PISSN: 01928651     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1096-987X(19990115)20:1<114::AID-JCC12>3.0.CO;2-L     Document Type: Article

References (192)

1. (a) Dreizier, R. M.; Gross, E. K. U. Density Functional Theory, An approach to the Quantum Many-Body Problem; Springer: Berlin, 1990;
2. (b) Parr, R. G.; Yang, W. Density-Functional Theory of Atoms and Molecules; Oxford University Press: New York, 1989;
3. (c) Dunitz, J. D.; Hafner, K.; Houk, K. N.; Ito, S.; Lehn, J.-M.; Raymond, K. N.; Rees, C. W.; Thiem, J.; Vögtle, F. Topics in Current Chemistry, Vois. 180, 181; Springer: Berlin, 1996;
4. (d) Hohenberg, P.; Kohn, W. Phys Rev 1964, 136, 864;
5. (e) Kohn, W.; Sham, L. J. Phys Rev A 1965, 140, 1133.
6. (a) Ziegler, T. Can J Chem 1995, 73, 743;
7. (b) Ziegler, T. Chem Rev 1991, 91, 651;
8. (c) Labanowski, J. K.; Andzelm, J. W. (Eds.), Density Functional Methods in Chemistry; Springer: New York, 1991;
9. (d) Laird, B. B.; Ross, R. B.; Ziegler, T. (Eds.) Chemical Applications of Density Functional Theory; American Chemical Society: Washington, DC, 1996;
10. (e) Dunitz, J. D.; Hafner, K.; Houk, K. N.; Ito, S.; Lehn, J.-M.; Raymond, K. N.; Rees, C. W.; Thiem, J.; Vögtle, F. Topics in Current Chemistry, Vols. 182 and 183; Springer: Berlin, 1996;
11. (f) Fonseca Guerra, C.; Snijders, J. G.; te Velde, G.; Baerends, E. J. Theor Chem Acc (in press);
12. (g) te Velde, G. Thesis, Vrije Universiteit, Amsterdam, The Netherlands, 1990;
13. (h) van den Hoek, P. J.; Kleyn, A. W.; Baerends, E. J. Comm Atom Mol Phys 1989, 23, 93.
14. (a) Curtiss, L. A.; Redfern, P. C.; Raghavachari, K.; Pople, J. A. J Chem Phys 1998, 109, 42;
15. (b) Redfern, P. C.; Blaudeau, J.-P.; Curtiss, L. A. J Phys Chem A 1997, 101, 8701;
16. (c) Becke, A. D. J Chem Phys 1993, 98, 1372, 5648;
17. (d) J Chem Phys 1993, 97, 9173;
18. (e) J Chem Phys 1992, 96, 2155;
19. (f) Murray, C.; Laming, N. C.; Handy, N. C.; Chem Phys Lett 1992, 199, 551;
20. (g) Perdew, J. P.; Chevary, J. A.; Vosko, S. H.; Jackson, K. A.; Pederson, M. R.; Singh, D. J.; Fiolhais, C. Phys Rev B 1992, 46, 6671.
21. Bickelhaupt, F. M.; Baerends, E. J. Rev Comput Chem (submitted).
22. (a) Hoffmann, R. Angew Chem 1982, 94, 725; Angew Chem Int Ed Engl 1982, 21, 711;
23. (a) Hoffmann, R. Angew Chem 1982, 94, 725; Angew Chem Int Ed Engl 1982, 21, 711;
24. (b) Hoffmann, R. Solids and Surfaces: A Chemists View of Bonding in Extended Structures; VCH: Weinheim, 1988.
25. (a) Rauk, A. Orbital Interaction Theory of Organic Chemistry; Wiley: New York, 1994;
26. (b) Albright, T. A.; Burdett, J. K.; Whangbo, M.-H. Orbital Interactions in Chemistry; Wiley: New York, 1985;
27. (c) Gimarc, B. M. Molecular Structure and Bonding; Academic: New York, 1979;
28. (d) Fleming, I. Frontier Orbitals and Organic Chemical Reactions; Wiley: London, 1976.
29. (a) Shaik, S. S. J Am Chem Soc 1981, 103, 3692;
30. (b) Pross, A.; Shaik, S. S. Acc Chem Res 1983, 16, 363;
31. (c) Shaik, S. S.; Schlegel, H. B.; Wolfe, S. Theoretical Aspects of Physical Organic Chemistry; Wiley: New York, 1992; Chapter 3;
32. Shaik, S.; Hiberty, P. C. Adv Quantum Chem 1995, 26, 99. See also:
33. (e) McWeeny, R. Methods of Molecular Quantum Mechanics; Academic: London, 1992; Chapter 7.
34. (a) Bickelhaupt, F. M.; Nibbering, N. M. M.; van Wezenbeek, E. M.; Baerends, E. J. J Phys Chem 1992, 96, 4864;
35. (b) Bickelhaupt, F. M.; Bickelhaupt, F. Chem Eur J (in press);
36. (c) Bickelhaupt, F. M.; Diefenbach, A.; de Visser, S. V.; de Koning, L. J.; Nibbering, N. M. M. J Phys Chem A (in press);
37. (d) Bickelhaupt, F. M.; Ziegler, T.; Schleyer, P. v. R. Organometallics 1996, 15, 1477;
38. (e) Bickelhaupt, F. M.; van Eikema Hommes, N. J. R.; Fonseca Guerra, C.; Baerends, E. J. Organometallics 1996, 15, 2923.
39. (a) Bickelhaupt, F. M.; Nibbering, N. M. M.; Baerends, E. J.; Ziegler, T. J Am Chem Soc 1993, 115, 9160;
40. (b) Bickelhaupt, F. M.; Baerends, E. J.; Nibbering, N. M. M. Chem Eur J 1996, 2, 196;
41. (c) Bickelhaupt, F. M.; Diefenbach, A.; Baerends, E. J.; (to be submitted);
42. (d) Bickelhaupt, F. M.; Ziegler, T.; Schleyer, P. v. R. Organometallics 1995, 14, 2288.
43. (a) Baerends, E. J.; Gritsenko, O. V. J Phys Chem A 1997, 101, 5383;
44. (b) Baerends, E. J.; Gritsenko, O. V.; van Leeuwen, R. In Tsipis, C. A.; Popov, V. S.; Herschbach, D. R.; Avery, J. A. (Eds.) New Methods in Quantum Theory, Vol. 8; Kluwer: Dordrecht, 1996;
45. (c) Baerends, E. J.; Gritsenko, O. V.; van Leeuwen, R. See ref. 2d, p. 20.
46. (a) Ziegler, T.; Rauk, A. Inorg Chem 1979, 18, 1558;
47. (b) Ziegler, T.; Rauk, A. Inorg Chem 1979, 18, 1755;
48. (c) Ziegler, T.; Rauk, A. Theor Chim Acta 1977, 46, 1.
49. (a) Morokuma, K. J Chem Phys 1971, 55, 1236;
50. (b) Kitaura, K.; Morokuma, K. Int J Quantum Chem 1976, 10, 325;
51. (c) Stone, A. J.; Erskine, R. W. J Am Chem Soc 1980, 102, 7185;
52. (d) Bernardi, F.; Bottoni, A.; Mangini, A.; Tonachini, G. J Molec Struct (Theochem) 1981, 86, 163;
53. (e) Post, D.; Baerends, E. J. J Chem Phys 1983, 78, 5663;
54. (f) Dapprich, S.; Frenking, G. J Phys Chem 1995, 99, 9352.
55. (a) Lowry, T. H.; Richardson, K. S. Mechanism and Theory in Organic Chemistry, 2nd Ed.; Harper and Row: New York, 1981;
56. (b) Carey, F. A.; Sundberg, R. J. Advanced Organic Chemistry, Part A; Plenum: New York, 1984;
57. (c) March, J. Advanced Organic Chemistry, 4th Ed., Wiley: New York, 1992;
58. (d) Isaacs, N. S. Physical Organic Chemistry, 2nd Ed., Longman: Harlow, UK, 1995.
59. (e) Reichardt, C. Solvents and Solvent Effects in Organic Chemistry, 2nd Ed., VCH: Weinheim, 1988.
60. (a) Bartsch, R. A.; Závada, J. Chem Rev 1980, 80, 453;
61. (b) Baciocchi, E. Acc Chem Res 1979, 12, 430;
62. (c) Saunders, W. H., Jr. Acc Chem Res 1976, 9, 19;
63. (d) Bunnett, J. F. Angew Chem 1962, 74, 731;
64. (e) Cram, D. J.; Greene, F. D.; DePuy, C. H. J Am Chem Soc 1956, 78, 790;
65. (f) McLennan, D. J. Tetrahedron 1975, 31, 2999;
66. (g) Biale, G.; Cook, D.; Lloyd, D. J.; Parker, A. J.; Stevens, I. D. R.; Takahashi, J.; Winstein, S. J Am Chem Soc 1971, 93, 4735;
67. (h) Parker, A. J.; Ruane, M.; Biale, G.; Winstein, S. Tetrahed Lett 1968, 2113;
68. Pirinccioglu, N.; Thibblin, A. J Am Chem Soc 1998, 120, 6512;
69. (j) Meng, Q.; Thibblin, A. J Am Chem Soc 1995, 117, 9399.
70. (a) Bickelhaupt, F. M.; Buisman, G. H. J.; de Koning, L. J.; Nibbering, N. M. M.; Baerends, E. J. J Am Chem Soc 1995, 117, 9889;
71. (b) Bickelhaupt, F. M. Reel Trav Chim Pays-Bas 1993, 112, 469;
72. (c) Bickelhaupt, F. M.; de Koning, L. J.; Nibbering, N. M. M. J Org Chem 1993, 58, 2436;
73. (d) Occhiucci, G.; Speranza, M.; de Koning, L. J.; Nibbering, N. M. M. J Am Chem Soc 1989, 111, 7387;
74. (e) de Koning, L. J. Nibbering, N. M. M. J Am Chem Soc 1987, 109, 1715.
75. (a) DeTuri, V. F.; Hintz, P. A.; Ervin, K. M. J Phys Chem A 1997, 101, 5969;
76. (b) Li, C.; Ross, P.; Szulejko, J. E.; McMahon, T. B. J Am Chem Soc 1996, 118, 9360;
77. (c) Rabasco, J. J.; Gronert, S.; Kass, S. R. J Am Chem Soc 1994, 116, 3133;
78. (d) Lum, R. C.; Grabowski, J. J. J Am Chem Soc 1992, 114, 9663;
79. (e) Grabowski, J. J.; Lum, R. C. J Am Chem Soc 1990, 112, 607;
80. (f) DePuy, C. H.; Gronert, S.; Mullin, A.; Bierbaum, V. M. J Am Chem Soc 1990, 122, 8650;
81. (g) Jones, M. E.; Ellison, G. B. J Am Chem Soc 1989, 111, 1645;
82. (h) Bierbaum, V. M.; Filley, J.; DePuy, C. H.; Jarrold, M. F.; Bowers, M. T. J Am Chem Soc 1985, 107, 2818;
83. (i) Ridge, D. P.; Beauchamp, J. L. J Am Chem Soc 1974, 96, 637.
84. (a) Nibbering, N. M. M. Acc Chem Res 1990, 23, 279;
85. (b) Riveros, J. M.; José, S. M.; Takashima, K. Adv Phys Org Chem 1985, 21, 197;
86. (c) Olmstead, W. N.; Brauman, J. I. J Am Chem Soc 1977, 99, 4219;
87. (d) Graul, S. T.; Bowers, M. T. J Am Chem Soc 1991, 113, 9696;
88. (e) Cyr, D. M.; Posey, L. A.; Bishea, G. A.; Han, C.-C.; Johnson, M. A. J Am Chem Soc 1991, 113, 9697;
89. (f) Wilbur, J. L.; Brauman, J. I. J Am Chem Soc 1991, 113, 9699.
90. N2 substitution.
91. N2 substitution.
92. (a) Nielsen, P. A.; Glad, S. S.; Jensen, F. J Am Chem Soc 1996, 118, 10577;
93. (b) Hu, W.-P.; Truhlar, D. G. J Am Chem Soc 1996, 118, 860;
94. (c) Glad, S. S.; Jensen, F. J Am Chem Soc 1994, 116, 9302;
95. (d) Gronert, S.; Kass, S. R. J Org Chem 1997, 62, 7991;
96. (e) Merrill, G. N.; Gronert, S.; Kass, S. R. J Phys Chem A 1997, 101, 208;
97. (f) Gronert, S. J Am Chem Soc 1993, 115, 652;
98. (g) J Am Chem Soc 1992, 114, 2349;
99. (h) J Am Chem Soc 1991, 113, 6041;
100. (i) Dewar, M. J. S.; Yuan, Y.-C. J Am Chem Soc 1990, 112, 2088, 2095;
101. (j) Minato, T.; Yamabe, S. J Am Chem Soc 1988, 110, 4586;
102. (k) J Am Chem Soc 1985, 107, 4621;
103. (l) Pross, A.; Shaik, S. S. J Am Chem Soc 1982, 104, 187.
104. (a) Clary, D. C.; Palma, J. J Chem Phys 1997, 106, 575;
105. (b) Glukhovtsev, M. N.; Pross, A.; Schlegel, H. B.; Bach, R. D.; Radom, L. J Am Chem Soc 1996, 118, 11258;
106. (c) Deng, L.; Branchadell, V.; Ziegler, T. J Am Chem Soc 1994, 116, 10645;
107. (d) Poirier, R. A.; Wang, Y.; Westatway, K. C. J Am Chem Soc 1994, 116, 2526;
108. (e) Sini, G.; Shaik, S.; Hiberty, P. C. J Chem Soc Perkin Trans 2 1992, 1019;
109. (f) Shi, Z.; Boyd, R. J. J Am Chem Soc 1991, 113, 1072;
110. (g) Vande Linde, S. R.; Hase, W. L. J Phys Chem 1990, 94, 6148;
111. (h) Carrion, F.; Dewar, M. J. S. J Am Chem Soc 1984, 106, 3531;
112. (i) Wolfe, S.; Mitchell, D. J.; Schlegel, H. B. J Am Chem Soc 1981, 103, 7692, 7694.
113. (a) Ferguson, H. A.; Ferguson, J. D.; Holmes, B. E. J Phys Chem 1998, 102, 5393;
114. (b) Kato, S.; Morokuma, K. J Chem Phys 1980, 73, 3900.
115. In addition, the leaving group is further removed from and therefore has less electrostatic repulsion with the attacking base in the anti-E2 transition state.
116. For experimental work on microsolvation, see: (a) Seeley, J. V.; Morris, R. A.; Viggiano, A. A.; Wang, H.; Hase, W. L. J Am Chem Soc 1997, 119, 577;
117. (b) O'Hair, R. A. J.; Davico, G. E.; Hacaloglu, J.; Dang, T. T.; DePuy, C. H.; Bierbaum, V. M. J Am Chem Soc 1994, 116, 3609;
118. (c) Freriks, I. L.; de Koning, L. J.; Nibbering, N. M. M.; J Org Chem 1992, 57, 5976;
119. (d) van der Wel, H.; Nibbering, N. M. M.; Sheldon, J. C.; Hayes, R. N.; Bowie, J. H. J Am Chem Soc 1987, 109, 5823;
120. (e) Hierl, P. M.; Ahrens, A. F.; Henchman, M.; Viggiano, A. A.; Paulson, J. F.; Clary, D. C. J Am Chem Soc 1986, 108, 3142;
121. (f) Henchman, M.; Hierl, P. M.; Paulson, J. F. J Am Chem Soc 1985, 107, 2812;
122. (g) Bohme, D. K.; Raksit, A. B. Can J Chem 1985, 63, 3007;
123. (h) Bohme, D. K.; Raksit, A. B. J Am Chem Soc 1984, 106, 3447;
124. (i) Henchman, M.; Paulson, J. F.; Hierl, P. M. J Am Chem Soc 1983, 105, 5509;
125. (j) Bohme, D. K.; Mackay, G. I. J Am Chem Soc 1981, 103, 978.
126. For other theoretical work on microsolvation, see: (a) Hirao, K.; Kebarle, P. Can J Chem 1989, 67, 1261; (b) Ohta, K.; Morokuma, K. J Phys Chem 1985, 89, 5845; (c) Dewar, M. J. S.; Storch, D. M. J Chem Soc Chem Commun 1985, 94; (d) Jaume, J.; Lluch, J. M.; Oliva, A.; Bertrán, J. Chem Phys Lett 1984, 106, 232; (e) Yamabe, S.; Yamabe, E.; Minato, T. J Chem Soc Perkin Trans 2 1983, 1881. (f) Morokuma, K. J Am Chem Soc 1982, 104, 3732; (g) Novoa, J. J.; Mota, F.; Perez del Valle, C.; Planas, M. J Phys Chem 1997, 101, 7842.
127. For other theoretical work on microsolvation, see: (a) Hirao, K.; Kebarle, P. Can J Chem 1989, 67, 1261; (b) Ohta, K.; Morokuma, K. J Phys Chem 1985, 89, 5845; (c) Dewar, M. J. S.; Storch, D. M. J Chem Soc Chem Commun 1985, 94; (d) Jaume, J.; Lluch, J. M.; Oliva, A.; Bertrán, J. Chem Phys Lett 1984, 106, 232; (e) Yamabe, S.; Yamabe, E.; Minato, T. J Chem Soc Perkin Trans 2 1983, 1881. (f) Morokuma, K. J Am Chem Soc 1982, 104, 3732; (g) Novoa, J. J.; Mota, F.; Perez del Valle, C.; Planas, M. J Phys Chem 1997, 101, 7842.
128. For other theoretical work on microsolvation, see: (a) Hirao, K.; Kebarle, P. Can J Chem 1989, 67, 1261; (b) Ohta, K.; Morokuma, K. J Phys Chem 1985, 89, 5845; (c) Dewar, M. J. S.; Storch, D. M. J Chem Soc Chem Commun 1985, 94; (d) Jaume, J.; Lluch, J. M.; Oliva, A.; Bertrán, J. Chem Phys Lett 1984, 106, 232; (e) Yamabe, S.; Yamabe, E.; Minato, T. J Chem Soc Perkin Trans 2 1983, 1881. (f) Morokuma, K. J Am Chem Soc 1982, 104, 3732; (g) Novoa, J. J.; Mota, F.; Perez del Valle, C.; Planas, M. J Phys Chem 1997, 101, 7842.
129. For other theoretical work on microsolvation, see: (a) Hirao, K.; Kebarle, P. Can J Chem 1989, 67, 1261; (b) Ohta, K.; Morokuma, K. J Phys Chem 1985, 89, 5845; (c) Dewar, M. J. S.; Storch, D. M. J Chem Soc Chem Commun 1985, 94; (d) Jaume, J.; Lluch, J. M.; Oliva, A.; Bertrán, J. Chem Phys Lett 1984, 106, 232; (e) Yamabe, S.; Yamabe, E.; Minato, T. J Chem Soc Perkin Trans 2 1983, 1881. (f) Morokuma, K. J Am Chem Soc 1982, 104, 3732; (g) Novoa, J. J.; Mota, F.; Perez del Valle, C.; Planas, M. J Phys Chem 1997, 101, 7842.
130. For other theoretical work on microsolvation, see: (a) Hirao, K.; Kebarle, P. Can J Chem 1989, 67, 1261; (b) Ohta, K.; Morokuma, K. J Phys Chem 1985, 89, 5845; (c) Dewar, M. J. S.; Storch, D. M. J Chem Soc Chem Commun 1985, 94; (d) Jaume, J.; Lluch, J. M.; Oliva, A.; Bertrán, J. Chem Phys Lett 1984, 106, 232; (e) Yamabe, S.; Yamabe, E.; Minato, T. J Chem Soc Perkin Trans 2 1983, 1881. (f) Morokuma, K. J Am Chem Soc 1982, 104, 3732; (g) Novoa, J. J.; Mota, F.; Perez del Valle, C.; Planas, M. J Phys Chem 1997, 101, 7842.
131. For other theoretical work on microsolvation, see: (a) Hirao, K.; Kebarle, P. Can J Chem 1989, 67, 1261; (b) Ohta, K.; Morokuma, K. J Phys Chem 1985, 89, 5845; (c) Dewar, M. J. S.; Storch, D. M. J Chem Soc Chem Commun 1985, 94; (d) Jaume, J.; Lluch, J. M.; Oliva, A.; Bertrán, J. Chem Phys Lett 1984, 106, 232; (e) Yamabe, S.; Yamabe, E.; Minato, T. J Chem Soc Perkin Trans 2 1983, 1881. (f) Morokuma, K. J Am Chem Soc 1982, 104, 3732; (g) Novoa, J. J.; Mota, F.; Perez del Valle, C.; Planas, M. J Phys Chem 1997, 101, 7842.
132. For other theoretical work on microsolvation, see: (a) Hirao, K.; Kebarle, P. Can J Chem 1989, 67, 1261; (b) Ohta, K.; Morokuma, K. J Phys Chem 1985, 89, 5845; (c) Dewar, M. J. S.; Storch, D. M. J Chem Soc Chem Commun 1985, 94; (d) Jaume, J.; Lluch, J. M.; Oliva, A.; Bertrán, J. Chem Phys Lett 1984, 106, 232; (e) Yamabe, S.; Yamabe, E.; Minato, T. J Chem Soc Perkin Trans 2 1983, 1881. (f) Morokuma, K. J Am Chem Soc 1982, 104, 3732; (g) Novoa, J. J.; Mota, F.; Perez del Valle, C.; Planas, M. J Phys Chem 1997, 101, 7842.
133. (a) Hu, W.-P.; Truhlar, D. G. J Am Chem Soc 1994, 116, 7797;
134. (b) Zhao, X. G.; Tucker, S. C.; Truhlar, D. G. J Am Chem Soc 1991, 113, 826;
135. (c) Tucker, S. C.; Truhlar, D. G. J Am Chem Soc 1990, 112, 3338, 3347.
136. Occhiucci, G.; Speranza, M.; de Koning, L. J.; Nibbering, N. M. M. J Am Chem Soc 1989, 111, 7387.
137. (a) Elschenbroich, C.; Salzer, A. Organometallics. A Concise Introduction, 2nd Ed.; VCH: Weinheim, 1992;
138. (b) Collman, J. P.; Hegedus, L. S.; Norton, J. R.; Finke, R. G. Principles and Applications of Organotransition Metal Chemistry; University Science Books: Mill Valley, CA, 1987.
139. (a) Rendina, L. M.; Puddephatt, R. J. Chem Rev 1997, 97, 1735;
140. (b) Gandelman, M.; Vigalok, A.; Shimon, L. J. W.; Milstein, D. Organometallics 1997, 16, 3981;
141. (c) Wick, D. D.; Goldberg, K. I. J Am Chem Soc 1997, 119, 10235;
142. (d) Crab-tree, R. H. Chem Rev 1995, 95, 987;
143. (e) Grushin, V. V.; Alper, H. Chem Rev 1994, 94, 1047;
144. (f) Wright, M. W.; Smalley, T. L.; Welker, M. E.; Rheingold, A. L. J Am Chem Soc 1994, 116, 6777;
145. (g) Sakakura, T.; Sodeyama, T.; Sasaki, K.; Wada, K.; Tanaka, M. J Am Chem Soc 1990, 112, 7221;
146. (h) Casalnuovo, A. L.; Calabrese, J. C.; Milstein, D. J Am Chem Soc 1988, 110, 6738;
147. (i) Janowicz, A. H.; Bergman, R. G. J Am Chem Soc 1983, 105, 3929.
148. (a) Schwarz, J.; Heinemann, C.; Schröder, D.; Schwarz, H. Helv Chim Acta 1996, 79, 1;
149. (b) Carpenter, C. J.; van Koppen, P. A. M.; Bowers, M. T. J Am Chem Soc 1995, 117, 10976;
150. (c) Chen, Y.-M.; Clemmer, D. E.; Armentrout, P. B. J Am Chem Soc 1994, 116, 7815;
151. (d) Wesendrup, R.; Schröder, D.; Schwarz, H. Angew Chem 1994, 105, 1232;
152. (e) van den Berg, K. J.; Ingemann, S.; Nibbering, N. M. M.; Gregor, I. K.; Rapid Common Mass Spectrom 1993, 7, 769;
153. (f) Eller, K.; Schwarz, H. Chem Rev 1991, 91, 1121;
154. (g) Armentrout, P. B.; Beauchamp, J. L. Acc Chem Res 1989, 22, 315.
155. (a) Chowdhury, A. K.; Wilkins, C. L. J Am Chem Soc 1987, 109, 5336;
156. (b) Weil, D. A.; Wilkins, C. L. J Am Chem Soc 1985, 107, 7316;
157. (c) Jones, R. W.; Staley, R. H. J Phys Chem 1982, 86, 1669;
158. (d) Jones, R. W.; Staley, R. H. J Am Chem Soc 1980, 102, 3794.
159. (a) Chertihin, G. V.; Andrews, L. J Am Chem Soc 1994, 116, 8322;
160. (b) Ritter, D.; Weisshaar, J. C. J Am Chem Soc 1990, 112, 6425;
161. (c) Mitchell, S. A.; Hackett, P. A. J Chem Phys 1990, 93, 7822.
162. (a) Bickelhaupt, F. M.; Radius, U.; Ehlers, A. W.; Hoffmann, R.; Baerends, E. J. New J Chem 1998, 1;
163. (b) Radius, U.; Bickelhaupt, F. M.; Ehlers, A. W.; Goldberg, N.; Hoffmann, R. Inorg Chem 1998, 37, 1080;
164. (c) Cotton, F. A.; Feng, X. J Am Chem Soc 1997, 119, 7514;
165. (d) Yoshizawa, K.; Ohta, T.; Yamabe, T.; Hoffmann, R. J Am Chem Soc 1997, 119, 12311;
166. (e) Ehlers, A. W.; Dapprich, S.; Vyboishchikov, S. F.; Frenking, G. Organometallics 1996, 15, 105;
167. (f) Irikura, K. K.; Goddard, W. A., III. J Am Chem Soc 1994, 116, 8733;
168. (g) Perry, J. K.; Goddard, W. A., III. J Am Chem Soc 1994, 116, 5013;
169. (h) Bickelhaupt, F. M.; Baerends, E. J.; Ravenek, W. Inorg Chem 1990, 29, 350;
170. (i) Koga, N.; Morokuma, K. Chem Rev 1991, 91, 823;
171. (j) Ziegler, T.; Tschinke, V.; Fan, L.; Becke, A. D. J Am Chem Soc 1989, 111, 9177.
172. (a) Griffin, T. R.; Cook, D. B.; Haynes, A.; Pearson, J. M.; Monti, D.; Morris, G. E. J Am Chem Soc 1996, 118, 3029;
173. (b) Aullón, G.; Alvarez, S. Inorg Chem 1996, 35, 3137;
174. (c) Hinderling, C.; Feichtinger, D.; Plattner, D. A.; Chen, P. J Am Chem Soc 1997, 119, 10793;
175. (d) Cui, Q.; Musaev, D. G.; Morokuma, K. J Chem Phys 1998, 108, 8418;
176. (e) Su, M.-D.; Chu, S.-Y. Inorg Chem 1998, 37, 3400.
177. (a) Hendrickx, M.; Ceulemans, M.; Gong, K.; Vanquicken-borne, L. J Phys Chem A 1997, 101, 8540;
178. (b) Perry, J. K.; Ohanessian, G.; Goddard, W. A., III. Organometallics 1994, 13, 1870;
179. (c) Siegbahn, P. E. M. Organometallics 1994, 13, 2833;
180. (d) Siegbahn, P. E. M.; Blomberg, M. R. A.; Svensson, M. J Am Chem Soc 1993, 115, 1952.
181. (a) Siegbahn, P. E. M. J Am Chem Soc 1994, 116, 7722;
182. (b) Siegbahn, P. E. M.; Blomberg, M. R. A.; Svensson, M. J Phys Chem 1993, 97, 2564;
183. (c) Blomberg, M. R. A.; Siegbahn, P. E. M.; Svensson, M. Inorg Chem 1993, 32, 4218;
184. (d) Siegbahn, P. E. M.; Blomberg, M. R. A.; Svensson, M. J Am Chem Soc 1993, 115, 4191;
185. (e) Blomberg, M. R. A.; Siegbahn, P. E. M.; Svensson, M. J Am Chem Soc 1992, 114, 6095;
186. (f) Svensson, M.; Blomberg, M. R. A.; Siegbahn, P. E. M. J Am Chem Soc 1991, 113, 7076.
187. (a) Ref. 27b, Chapter 12;
188. (b) Hickey, C. E.; Maitlis, P. M. J Chem Soc Chem Commun 1984, 1609;
189. (c) Forster, D. Adv Organometal Chem 1979, 17, 255;
190. (d) Forster, D. J Am Chem Soc 1975, 97, 951;
191. (e) J Am Chem Soc 1976, 98, 846.
192. Bickelhaupt, F. M. Unpublished results.