Tetra-tert-butylethylene: An elusive molecule with a highly twisted double bond. Can it be made by carbene dimerization?

Journal of the American Chemical Society

Volumn 118, Issue 41, 1996, Pages 9908-9914

  Sulzbach, Horst M ^a,b   Bolton, Evan ^a   Lenoir, Dieter ^c   Schleyer, Paul V R ^a,b,d   Schaefer III, Henry F ^a,d  

^a UNIVERSITY OF GEORGIA   (United States)

^b UNIVERSITY OF ERLANGEN NUREMBERG   (Germany)

^c INSTITUTE OF EPIDEMIOLOGY   (Germany)

^d Ctr for Compl Quantum Chemistry   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ETHYLENE DERIVATIVE;

ARTICLE; DRUG STRUCTURE; MOLECULAR DYNAMICS; POLYMERIZATION; THEORY;

EID: 0029859339     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja960549r     Document Type: Article

References (75)

1. For reviews on strained molecules, see: (a) Tidwell, T. T. Tetrahedron 1978, 34, 1855. (b) Liebman, J. F.; Greenberg, A. Strained Organic Molecules; Academic Press: New York, 1978. (c) Lenoir, D. Nachr. Chem. Techn. Lab. 1979, 27, 762. (d) Sandström, J. Topics in Stereochemistry; Wiley, J.: New York, 1983; Vol. 14, pp 183-230. (d) Chem. Rev. 1989, 5, 973. (e) Luef, W.; Keese, R. Top. Stereochem. 1991, 20, 231.
2. For reviews on strained molecules, see: (a) Tidwell, T. T. Tetrahedron 1978, 34, 1855. (b) Liebman, J. F.; Greenberg, A. Strained Organic Molecules; Academic Press: New York, 1978. (c) Lenoir, D. Nachr. Chem. Techn. Lab. 1979, 27, 762. (d) Sandström, J. Topics in Stereochemistry; Wiley, J.: New York, 1983; Vol. 14, pp 183-230. (d) Chem. Rev. 1989, 5, 973. (e) Luef, W.; Keese, R. Top. Stereochem. 1991, 20, 231.
3. For reviews on strained molecules, see: (a) Tidwell, T. T. Tetrahedron 1978, 34, 1855. (b) Liebman, J. F.; Greenberg, A. Strained Organic Molecules; Academic Press: New York, 1978. (c) Lenoir, D. Nachr. Chem. Techn. Lab. 1979, 27, 762. (d) Sandström, J. Topics in Stereochemistry; Wiley, J.: New York, 1983; Vol. 14, pp 183-230. (d) Chem. Rev. 1989, 5, 973. (e) Luef, W.; Keese, R. Top. Stereochem. 1991, 20, 231.
4. For reviews on strained molecules, see: (a) Tidwell, T. T. Tetrahedron 1978, 34, 1855. (b) Liebman, J. F.; Greenberg, A. Strained Organic Molecules; Academic Press: New York, 1978. (c) Lenoir, D. Nachr. Chem. Techn. Lab. 1979, 27, 762. (d) Sandström, J. Topics in Stereochemistry; Wiley, J.: New York, 1983; Vol. 14, pp 183-230. (d) Chem. Rev. 1989, 5, 973. (e) Luef, W.; Keese, R. Top. Stereochem. 1991, 20, 231.
5. For reviews on strained molecules, see: (a) Tidwell, T. T. Tetrahedron 1978, 34, 1855. (b) Liebman, J. F.; Greenberg, A. Strained Organic Molecules; Academic Press: New York, 1978. (c) Lenoir, D. Nachr. Chem. Techn. Lab. 1979, 27, 762. (d) Sandström, J. Topics in Stereochemistry; Wiley, J.: New York, 1983; Vol. 14, pp 183-230. (d) Chem. Rev. 1989, 5, 973. (e) Luef, W.; Keese, R. Top. Stereochem. 1991, 20, 231.
6. For reviews on strained molecules, see: (a) Tidwell, T. T. Tetrahedron 1978, 34, 1855. (b) Liebman, J. F.; Greenberg, A. Strained Organic Molecules; Academic Press: New York, 1978. (c) Lenoir, D. Nachr. Chem. Techn. Lab. 1979, 27, 762. (d) Sandström, J. Topics in Stereochemistry; Wiley, J.: New York, 1983; Vol. 14, pp 183-230. (d) Chem. Rev. 1989, 5, 973. (e) Luef, W.; Keese, R. Top. Stereochem. 1991, 20, 231.
7. For recent reviews, see: (a) Lenoir, D. Synthesis 1989, 883. (b) McMurry, J. E. Chem. Rev. 1989, 89, 1513.
8. For recent reviews, see: (a) Lenoir, D. Synthesis 1989, 883. (b) McMurry, J. E. Chem. Rev. 1989, 89, 1513.
9. Bomse, D. S.; Morton, T. H. Tetrahedron Lett. 1975, 781.
10. Langler, R. F.; Tidwell, T. T. Tetrahedron Lett. 1975, 777.
11. Olah, G. A.; Prakash, G. K. S. J. Org. Chem. 1977, 42, 580.
12. Lenoir, D.; Malwitz, D.; Meyer, B. Tetrahedron Lett. 1984, 2965.
13. Doering, W. v. E.; Roth, W. R.; Bauer, F.; Breuckmann, R.; Ebbrecht, T.; Herbold, M.; Schmidt, R.; Lennartz, H.-W.; Lenoir, D.; Böse, R. Chem. Ber. 1989, 122, 1263.
14. Lenoir, D.; Burghard, H. J. Chem. Res. 1980, (S) 396, (M) 471.
15. Kalinowski, H.-O.; Röcker, E.; Maier, G. Org. Magn. Res. 1983, 21, 64.
16. Gano, J. E.; Wettach, R. H.; Platz, M. S.; Senthilnathan, V. P. J. Am. Chem. Soc. 1982, 104, 2326.
17. Bock, H.; Berkner, B.; Hierholzer, B.; Jaculi, D. Helv. Chim. Acta 1992, 75, 1798.
18. Barton, D. H. R.; Willis, B. J. J. Chem. Soc., Perkin Trans. 1 1972, 305.
19. Barton, D. H. R.; Guziec, F. S.; Shahak, I. J. Chem. Soc., Perkin Trans. 1 1974, 1794.
20. Back, T. G.; Barton, D. H. R.; Britten-Kelly, M. R.; Guziec, F. S. J. Chem. Soc., Perkin Trans. 1 1976, 2079.
21. Buter, J.; Wassenaar, S.; Kellogg, R. M. J. Org. Chem. 1972, 37, 4045.
22. Herbold, M. Dissertation, University of Bochum, Bochum, Germany, 1989.
23. Loerzer, T.; Gerke, R.; Lüttke, W. Tetrahedron Lett. 1983, 24, 5861.
24. Brooks, P. R.; Bishop, R.; Counter, J. A.; Tiekinik, E. R. T. J. Org. Chem. 1994, 59, 1365.
25. Back, T. G.; Barton, D. H. R.; Britten-Kelly, M. R.; Guziec, F. S. J. Chem. Soc., Perkin Trans. 1 1975, 539.
26. Krebs, A.; Rüger, W.; Nickel, W.-U. Tetrahedron Lett. 1981, 22, 4563.
27. Krebs, A.; Born, W.; Kaletta, B.; Nickel, W.-U.; Rüger, W. Tetrahedron Lett. 1983, 24, 4821.
28. Krebs, A.; Kaletta, B.; Nickel, W.-U.; Rüger, W.; Tikwe, L. Tetrahedron 1985, 42, 1693.
29. Guziec, F. S.; Murphy, C. J. J. Org. Chem. 1980, 45, 2890.
30. Cullen, E. R.; Guziec, F. S.; Hollander, M. I.; Murphy, C. J. Tetrahedron Lett. 1981, 22, 4563.
31. Cullen, E. R.; Guziec, F. S.; Murphy, C. J. J. Org. Chem. 1982, 47, 3563.
32. Cullen, E. R.; Guziec, F. S. J. Org. Chem. 1986, 51, 1212.
33. Garratt, P. J.; Payne, D.; Tocher, D. A. J. Org. Chem. 1990, 55, 1909.
34. Krebs, A.; Nickel, W.-U.; Tikwe, L.; Kopf, J. Tetrahedron Lett. 1985, 26, 1639.
35. Krebs, A., private communication.
36. Ermer, O.; Lifson, S. Tetrahedron 1974, 30, 2425.
37. (a) Krebs, A.; Rüger, W.; Nickel, W.-U.; Wilke, M.; Burkert, U. Chem. Ber. 1984, 117, 310.
38. (b) Ermer, O. Aspekte von Kraftfeldrechnungen; Bauer: München, 1981; p 248.
39. Lenoir, D.; Dauner, H.; Frank, R. M. Chem. Ber. 1980, 113, 2636.
40. Burkert, U. Tetrahedron 1981, 37, 333.
41. Favini, G.; Simonetta, M.; Todwschini, R. J. Comput. Chem. 1981, 2, 149.
42. Burkert, U.; Allinger, N. L. Molecular Mechanics; ACS Monograph 177; American Chemical Society: Washington, DC, 1982.
43. Roothaan, C. C. J. Rev. Mod. Phys. 1951, 23, 69.
44. Roothaan, C. C. J. Rev. Mod. Phys. 1960, 32, 179.
45. (a) Labanowski, J. W.; Andzelm, J.; Density Functional Methods in Chemistry; Springer; New York, 1991.
46. (b) Parr, R. G.; Yang, W. Density Functional Theory in Atoms and Molecules; Oxford University Press: New York, 1989.
47. CADPAC5: The Cambridge Analytic Derivatives Package Issue 5.2, Cambridge, England, 1994. A suite of quantum chemistry programs developed by R. D. Amos, N. C. Handy, and co-workers.
48. (a) Gaussian 92/DFT, Revision F.2. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Wong, M. W.; Foresman, J. B.; Robb, M. A.; Head-Gordon, M.; Replogle, E. S.; Gomperts, R.; Andres, J. L.; Raghavachari, K.; Binkley, J. S.; Gonzalez, C.; Martin, R. L.; Fox, D. J.; Defrees, D. J.; Baker, J.; Stewart, J. J. P.; Pople, J. A. Gaussian, Inc.: Pittsburgh, PA, 1993.
49. (b) Gaussian 92/DFT New Methods and Features in Gaussian 92/DFT; Gaussian Inc.: Pittsburgh, PA, 1993.
50. PSI2.0.8. Janssen, C. L.; Seidl, E. T.; Scuseria, G. E.; Hamilton, T. P.; Yamaguchi, Y.; Remington, R. B.; Xie, Y.; Vacek, G.; Sherrill, C. D.; Crawford, T. D.; Fermann, J. T.; Allen, W. D.; Brooks, B. R.; Fitzgerald, G. B.; Fox, D. J.; Gaw, J. F.; Handy, N. C.; Laidig, W. D.; Lee, T. J.; Pitzer, R. M.; Rice, J. E.; Saxe, P.; Scheiner, A. C.; Schaefer, H. F. PSITECH, Inc.: Watkminsville, GA, 1994.
51. Hehre, W. J.; Radom, L.; Pople, J. A.; Schleyer, P. v. R. Ab Initio Molecular Orbital Theory; John Wiley & Sons, Inc.: New York, 1986.
52. Huzinaga, S. J. Chem. Phys. 1965, 45, 1293.
53. Dunning, T. H. J. Chem. Phys. 1970, 53, 2823.
54. Dunning, T. H. J. Chem. Phys. 1971, 55, 716.
55. Figures 1-5 depict only half of molecule 1 for clarity.
56. We were unable to locate a minimum for 1 that employs transbending to reduce the strain.
57. At ROHF/DZd, the CC double bond length in ethylene is 1.325 Å compared to 1.351 Å at BLYP/DZd. Hence, at ROHF/DZd, the computed values for the strained CC double bond are expected to be slightly too small, while the CC bond lengths that are obtained at BLYP/DZd will be somewhat too large.
58. Beck, A.; Gompper, R.; Polborn, K.; Wagner, H.-U. Angew. Chem., Int. Ed. Engl. 1993, 32, 1352.
59. (a) See ref 43.
60. (b) The stability of the triplet electronic state is overestimated at the ROHF level because the triplet has one less doubly occupied MO than the singlet. Since electron correlation is neglected, the HF level gives a nonrealistically low energy for the triplet as compared to the singlet.
61. Wiberg, K. B.; Hadad, C. M.; Foresman, J. B.; Chupka, W. A. J. Phys. Chem. 1992, 96, 10756.
62. (a) Robin, M. B. Higher Excited States of Polyatomic Molecules; Academic Press: New York, 1985; Vol. III.
63. (b) Doering, W. v. E.; Roth, W. R.; Lenoir, D.; Boese, R. Chem. Ber. 1989, 122, 1263.
64. An older value of 63.5 kcal/mol is given by: Douglas, J. E.; Rabinovitch, B. S.; Looney, F. S. J. Chem. Phys. 1955, 23, 315.
65. Nickon, A. Acc. Chem. Res. 1993, 26, 84.
66. Armstrong, B. M.; McKee, M L.; Shevlin, P. B. J. Am. Chem. Soc. 1995, 117, 3685.
67. Pauncz, R. Spin Eigenfunctions; Plenum Press: New York, 1979; pp 1-7.
68. Only the central six carbon atoms of the transition state are shown. The rest of the molecule has been omitted for reasons of clarity.
69. With respect to singlet 6.
70. McKellar, A. R. W.; Bunker, P. R.; Sears, T. J.; Evenson, K. M.; Saykally, R. J.; Langhoff, S. R. J. Chem. Phys. 1983, 79, 5251.
71. Including ZPVE computed at Becke3LYP/6-31G*.
72. 3, see: Richards, C. A., Jr.; Kim, S.-J.; Yamaguchi, Y.; Schaefer, H. F. J. Am. Chem. Soc. 1995, 117, 10104.
73. Detailed tables are provided in the Supporting Information.
74. 54 compute triplet 8 to be 1-2 kcal/mol lower than singlet 8 at QCISD(T)/6-31+G(2d,p)// MP2/6-31G(d).
75. Khodabandeh, S.; Carter, E. A. J. Phys. Chem. 1993, 97, 4360.