Why cyclooctatetraene is highly stabilized: The importance of "two-way" (double) hyperconjugation

Journal of Chemical Theory and Computation

Volumn 8, Issue 4, 2012, Pages 1280-1287

  Wu, Judy I ^a   Fernández, Israel ^b   Mo, Yirong ^c   Von Ragué Schleyer, Paul ^a  

^a UNIVERSITY OF GEORGIA   (United States)

^b UNIVERSIDAD COMPLUTENSE DE MADRID   (Spain)

^c WESTERN MICHIGAN UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 84859611710     PISSN: 15499618     EISSN: 15499626     Source Type: Journal    
DOI: 10.1021/ct3000553     Document Type: Article

References (110)

1. Willstätter, R.; Waser, E. Chem. Ber. 1911, 44, 3423-3445
2. 2 d structure of COT lay in the future (see below), Willstätter assumed COT to have a planar structure and rationalized its unexpected olefinic (rather than aromatic) behavior by an imaginative (but now amusingly quaint) explanation. He invoked the "centric" benzene model of Claus (Claus, A. Theoretische Betrachtungen und deren Anwendungen zur Systematik der Organischen Chemie; Freiburg, Germany, 1867; p 207), Armstrong (Armstrong, H. E. J. Chem. Soc. 1887, 51, 258-268), and Baeyer (Baeyer, A. Ann. Chem. 1887, 245, 103-190; Ann. Chem. 1888, 251, 257-311), which assumed that the six "extra" valences of benzene extended from each of the carbons toward the ring center where they were "saturated" by their centric interactions. The 1/3 larger radius of the planar eight-membered COT ring diminished the possibility of centric "saturation" compared to that of the six-membered benzene ring. According to Willstätter, this difference was responsible for the olefinic behavior of the double bonds of COT.
3. Fray, G. I.; Saxton, R. G. In The Chemistry of Cyclo-octatetraene and its Derivatives; Cambridge University Press: Cambridge, 1978.
4. Raphael, R. A. Cyclooctatetraene. In Nonbenzenoid Aromatic Compounds; Interscience Publishers, Inc.: New York, 1959; p 465.
5. Balaban, A. T. Pure Appl. Chem. 1980, 52, 1409-1429
6. Snyder, J. P. In Nonbenzenoid Aromatics; Academic Press: New York, 1969; Vol. 1, p 29.
7. Thiele, J. Ann. Chem. 1899, 306, 87-142
8. Pierrefixe, S. C. A.; Bickelhaupt, F. M. J. Phys. Chem. A 2008, 112, 12816-12822
9. (See: Allinger, N. L.; Sprague, J. T.; Finder, C. J. Tetrahedron 1973, 29, 2519-2523
10. Roth, W. R.; Lennartz, H. W.; Vogel, E.; Leiendecker, M.; Oda, M. Chem. Ber. 1986, 119, 837-843
11. (See: Wannere, C. S.; Moran, D.; Allinger, N. L.; Hess, B. A., Jr.; Schaad, L. J.; Schleyer, P. v. R. Org. Lett. 2003, 17, 2983-2986
12. Schleyer, P. v. R.; Pühlhofer, F. Org. Lett. 2002, 4, 2873-2876
13. Wiberg, K. B. Chem. Rev. 2001, 101, 1317-1331
14. (See: Nevins, N.; Lii, J. H.; Allinger, N. L. J. Comput. Chem. 1996, 17, 695-729
15. Allinger, N. L. In Molecular Structure: Understanding Steric and Electronic Effects From Molecular Mechanics; John Wiley and Sons, Inc.: Hoboken, NJ, 2010; Chapter 5, pp 115-116.).
16. Stevenson, G. R. J. Chem. Educ. 1972, 49, 781-782
17. Karadakov, P. B. J. Phys. Chem. A 2008, 112, 12707-12713
18. Havenith, R. W. A.; Fowler, P. W.; Jenneskens, L. W. Org. Lett. 2006, 8, 1255-1258
19. Pauling, L. In The Nature of the Chemical Bond, 3 rd ed.; Cornell University Press: Ithaca, NY, 1960; p 196.
20. Politzer, P.; Murray, J. S.; Seminario, J. M. Int. J. Quantum Chem. 1994, 50, 273-277
21. Prosen, E. J.; Johnson, W. H.; Rossini, F. D. J. Am. Chem. Soc. 1947, 69, 2068-2069
22. d)(H) group increment based on fully conjugation-stabilized anti -dienes.
23. (See: Wodrich, M. D.; Wannere, C. S.; Mo, Y.; Jarowski, P. D.; Houk, K. N.; Schleyer, P. v. R. Chem. - Eur. J. 2007, 13, 7731-7744, for propene stabilization
24. (See: Cohen, N.; Benson, S. W. Chem. Rev. 1993, 93, 2419-2438)
25. Equation 4 is an evaluation based on the experimental heats of formation of COT (71.13 kcal/mol, from http://cccbdb.nist.gov/), cyclooctane (-29.7 kcal/mol, from Pedley, J. B.; Naylor, R. D.; Kirby, S. P. Thermochemical Data of Organic Compounds, 2 nd ed.; Chapman and Hall: New York, 1986,), and cis -cyclooctene (-4.57 kcal/mol, from
26. Schmitz, L. R.; Chen, Y. R. J. Comput. Chem. 1994, 15, 1437-1445)
27. Cope, A. C.; Overberger, C. G. J. Am. Chem. Soc. 1948, 70, 1433-1437
28. Traetteberg, M. Acta Chem. Scand. 1966, 20, 1724-1726
29. Bastiansen, O.; Hedberg, L.; Hedberg, K. J. Chem. Phys. 1957, 27, 1311-1317
30. Claus, K. H.; Krüger, C. Acta Crystallogr. 1988, C44, 1632-1634
31. Bordner, J.; Parker, R. G.; Stanford, R. H. Acta. Crystallogr., Sect. B 1972, 28, 1069-1074
32. Kaufman, H. S.; Fankuchen, I.; Mark, H. Nature 1948, 161, 165
33. Dominique, S. K.; Lobsiger, S.; Frey, H. M.; Leutwyler, S.; Stanton, J. F. J. Phys. Chem. A 2008, 112, 9134-9143
34. Craig, N. C.; Groner, P.; McKean, D. C. J. Phys. Chem. A 2006, 110, 7461-7469
35. Duncan, J. L.; McKean, D. C.; Bruce, A. J. J. Mol. Spectrosc. 1979, 74, 361-374
36. Dewar, M. J. S.; Schmeising, A. N. Tetrahedron 1956, 5, 166-178
37. Skaarup, S.; Boggs, J. E.; Scancke, P. N. Tetrahedron 1976, 32, 1179-1181
38. Klärner, F. G. Angew. Chem., Int. Ed. 2001, 40, 3977-3981
39. Ohmae, T.; Nishinaga, T.; Wu, M.; Iyoda, M. J. Am. Chem. Soc. 2010, 132, 1066-1074
40. Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1992, 114, 5879-5881
41. Borden, W. T.; Davidson, E. R. J. Am. Chem. Soc. 1977, 99, 4587-4594
42. Oth, J. F. M. Pure Appl. Chem. 1971, 25, 573-622
43. Baird, N. C. J. Am. Chem. Soc. 1972, 94, 4941-4948
44. Gogonea, V.; Schleyer, P. v. R.; Schreiner, P. R. Angew. Chem., Int. Ed. 1998, 37, 1945-1948
45. Wenthold, P. G.; Hrovat, D. A.; Borden, W. T.; Lineberger, W. C. Science 1996, 272, 1456-1459
46. Kato, S.; Lee, H. S.; Gareyev, R.; Wenthold, P. G.; Lineberger, W. C.; DePuy, C. H.; Bierbaum, V. M. J. Am. Chem. Soc. 1997, 119, 7863-7864
47. Anet, F. A. L. J. Am. Chem. Soc. 1962, 84, 671-672
48. Anet, F. A. L.; Bourn, A. J. R.; Lin, Y. S. J. Am. Chem. Soc. 1964, 86, 3576-3577
49. Daudey, J. P.; Trinquier, G.; Barthelat, J. C.; Malrieu, J. P. Tetrahedron 1980, 36, 3399-3401
50. Wiberg, K. B.; Rosenberg, R. E.; Rablen, P. R. J. Am. Chem. Soc. 1991, 113, 2890-2898
51. Feller, D.; Craig, N. C.; Matlin, A. R. J. Phys. Chem. A 2008, 112, 2131-2133
52. George, P.; Trachtman, M. C.; Bock, W.; Brett, A. M. Tetrahedron 1976, 32, 1357-1362
53. Mulliken, R. S. Tetrahedron 1959, 6, 68-87
54. Pitzer, K. S.; Guttman, L.; Westrum, E. F., Jr. J. Am. Chem. Soc. 1946, 68, 2209-2212
55. Mo, Y.; Gao, J. Acc. Chem. Res. 2007, 40, 113-119
56. Asturiol, D.; Salvador, P.; Mayer, I. Chem. Phys. Phys. Chem. 2009, 10, 1987-1992
57. Pendas, A. M.; Blanco, M. A.; Francisco, E. J. Comput. Chem. 2008, 30, 98-109
58. Su, P.; Li, H. J. Chem. Phys. 2009, 131, 014102
59. Esquivel, R. O.; Liu, S. B.; Angulo, J. C.; Dehesa, J. S.; Antolín, J.; Molina-Espíritu, M. J. Phys. Chem. A 2011, 115, 4406-4415
60. Mo, Y. WIREs Comput. Mol. Sci. 2011, 1, 164-171
61. Mo, Y. Nature 2010, 2, 666-671
62. Wu, W.; Ma, B.; Wu, J. I.; Schleyer, P. v. R.; Mo, Y. Chem. - Eur. J. 2009, 15, 9730-9736
63. Mo, Y.; Peyerimhoff, S. D. J. Chem. Phys. 1998, 109, 1687-1697
64. Mo, Y.; Zhang, Y.; Gao, J. J. Am. Chem. Soc. 1999, 121, 5737-5742
65. Mo, Y.; Subramanian, G.; Ferguson, D. M.; Gao, J. J. Am. Chem. Soc. 2002, 124, 4832-4837
66. Mo, Y.; Wu, W.; Song, L.; Lin, M.; Zhang, Q.; Gao, J. Angew. Chem. 2004, 116, 2020-2024
67. Angew. Chem., Int. Ed. 2004, 43, 1986-1990.
68. Mo, Y. J. Chem. Phys. 2003, 119, 1300-1306
69. Mo, Y.; Song, L.; Wu, W.; Zhang, Q. J. Am. Chem. Soc. 2004, 126, 3974-3982
70. Mo, Y. J. Org. Chem. 2004, 69, 5563-5567
71. Mo, Y.; Song, L.; Lin, Y. J. Phys. Chem. A 2007, 111, 8291-8301
72. Song, L.; Wu, W.; Mo, Y.; Zhang, Q. XMVB: Ab initio Non-orthogonal Valence Bond Program; Xiamen University: Xiamen, China, 2003.
73. Gamess (Version R5): Schmidt, M. W.; Baldridge, K. K.; Boatz., J. A.; Elbert, S. T.; Gordon, M. S.; Jensen, J. H.; Koseki, S.; Matsunaga, N.; Nguyen, K. A.; Su, S. J.; Windus, T. L.; Dupuis, M.; Montgomery, J. A. J. Comput. Chem. 1993, 14, 1347-1363
74. Andrés, J. L.; Castano, O.; Morreale, A.; Palmerio, R.; Gomperts, R. J. Chem. Phys. 1998, 108, 203-207
75. Alabugin, I. V.; Gilmore, K. M.; Peterson, P. W. WIREs Comput. Mol. Sci. 2011, 1, 109-141
76. Weinhold, F.; West, R. Organometallics 2011, 30, 5815-5824
77. Dederichs, P. H.; Bluegel, S.; Zeller, R.; Akai, H. Phys. Rev. Lett. 1984, 53, 2512-2515
78. Wu, Q.; Van Voorhis, T. J. Chem. Theory Comput. 2006, 2, 765-774
79. Khaliullin, R. Z.; Head-Gordon, M.; Bell, A. T. J. Chem. Phys. 2006, 124, 204105
80. Khaliullin, R. Z.; Cobar, E. A.; Lochan, R. C.; Bell, A. T.; Head-Gordon, M. J. Phys. Chem. A 2007, 111, 8753-8765
81. Kollmar, H. J. Am. Chem. Soc. 1979, 101, 4832-4840
82. Mo, Y.; Hiberty, P. C.; Schleyer, P. v. R. Theor. Chem. Acc. 2010, 127, 27-38
83. Zielinski, M.; Havenith, R. W. A.; Jenneskens, L. W.; Lenthe, J. H. v. Theor. Chem. Acc. 2010, 127, 19-25
84. Mo, Y.; Schleyer, P. v. R. Chem. - Eur. J. 2006, 12, 2009-2020
85. Mo., Y.; Gao, J.; Peyerimhoff, S. D. J. Chem. Phys. 2000, 112, 5530-5538
86. Mo, Y.; Bao, P.; Gao, J. Phys. Chem. Chem. Phys. 2011, 15, 6760-6775
87. Steinmann, S. N.; Jana, D. F.; Wu, J. I.; Schleyer, P. v. R.; Mo, Y.; Corminboeuf, C. Angew. Chem., Int. Ed. 2009, 48, 9828-9833
88. Mo, Y.; Bao, P.; Gao, J. Phys. Chem. Chem. Phys. 2011, 13, 6760-6775
89. Glendening, X.; E. D.; Badenhoop, J. K.; Reed, A. E.; Carpenter, J. E.; Bohmann, J. A.; Morales, C. M.; Weinhold, F. NBO 5; Theoretical Chemistry Institute, University of Wisconsin: Madison, WI, 2003.
90. Reed, A. E.; Curtis, L. A.; Wienhold, F. Chem. Rev. 1988, 88, 899-926
91. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.;; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03, revision C.02; Gaussian, Inc.: Wallingford, CT, 2004.
92. Gleiter, R.; Heilbronner, E.; Hekman, M.; Martin, H. D. Chem. Ber. 1973, 106, 28-34
93. Pelosi, L. F.; Miller, W. T. J. Am. Chem. Soc. 1976, 98, 4311-4312
94. Gleiter, R.; Karcher, M. Angew. Chem., Int. Ed. Engl. 1988, 27, 840-841
95. Roth, W. R.; Adamczak, O.; Breuckmann, R.; Lennartz, H. W.; Boese, R. Chem. Ber. 1991, 124, 2499-2521
96. Murcko, M. A.; Castejon, H.; Wiberg, K. B. J. Phys. Chem. 1996, 100, 16162-16168
97. Lauvergnat, D.; Hiberty, P. C. J. Am. Chem. Soc. 1997, 119, 9478-9482
98. Xi, H. W.; Karni, M. J. Phys. Chem. A 2008, 112, 13066-13079
99. Aue, D. H. WIREs Comput. Mol. Sci. 2011, 1, 487-508
100. Bastiansen, O. Acta Chem. Scand. 1949, 3, 408-414
101. Tsuzuki, S.; Uchimaru, T.; Matsumura, K.; Mikami, M.; Tanabe, K. J. Chem. Phys. 1999, 110, 2858-2861
102. Almenningen, A.; Bastiansen, O.; Fernholt, L.; Cyvin, B. N.; Cyvin, S. J.; Samdal, S. J. Mol. Struct. 1985, 128, 59-76
103. Bastiansen, O.; Samdal, S. J. Mol. Struct. 1985, 128, 115-125
104. Johansson, M. P.; Olsen, J. J. Chem. Theory Comput. 2008, 4, 1460-1471
105. Matta, C. F.; Trujillo, J. H.; Tang, T. H.; Bader, R. F. W. Chem. - Eur. J. 2003, 9, 1940-1951
106. Based on QTAIM, a bond critical point indicative of "H-H bonding" is present between the bay H's of planar biphenyl. See support for the classical viewpoint: Poater, J.; Visser, R.; Solá, M.; Bickelhaupt, F. M. J. Org. Chem. 2007, 72, 1134-1142
107. Cappel, D.; Tüllmann, S.; Krapp, A.; Frenking, G. Angew. Chem., Int. Ed. 2005, 44, 3617-3620
108. Fernández, I.; Frenking, G. Chem. - Eur. J. 2006, 12, 3617-3629
109. Xi, H. W.; Karni, M.; Apeloig, Y. J. Phys. Chem. A 2008, 112, 13066-13079
110. Martinez-Guajardo, G.; Gómez-Saldoval, Z.; Jana, D. F.; Calaminici, P.; Corminboeuf, C.; Merino, G. Phys. Chem. Chem. Phys. 2011, 13, 20615-20619