Calculations of the equilibrium isotope effects on the reductions of benzene-d6 and cyclooctatetraene-d8

Journal of the American Chemical Society

Volumn 119, Issue 40, 1997, Pages 9523-9526

  Hrovat, David A ^a   Hammons, J H ^b   Stevenson, Cheryl D ^c   Borden, Weston Thatcher ^a  

^a UNIVERSITY OF WASHINGTON   (United States)

^b SWARTHMORE COLLEGE   (United States)

^c ILLINOIS STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AROMATIC HYDROCARBON; BENZENE; ISOTOPE;

ARTICLE; CALCULATION; CHEMICAL BOND; CHEMICAL STRUCTURE; ELECTRON TRANSPORT; ENERGY; EQUILIBRIUM CONSTANT; REDUCTION;

EID: 0030728866     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9714144     Document Type: Article

References (44)

1. (a) Stevenson, C. D.; Espe, M. P.; Reiter, R. C. J. Am. Chem. Soc. 1986, 108, 533.
2. (b) Stevenson, C. D.; Espe, M. P.; Reiter, R. C. J. Am. Chem. Soc. 1986, 108, 5760.
3. Lauricella, T. L.; Pescatore, J. A.; Reiter, R. C., Stevenson, R. D.; Stevenson, C. D. J. Phys Chem. 1988, 92, 3687.
4. Stevenson, C. D.; Sturgeon, B. E.; Vines, S. K.; Peters, S. J. J. Phys Chem. 1988, 92, 6850.
5. (e) Stevenson, C. D.; Reidy, K. A.; Peters, S. J.; Reiter, R. C. J. Am. Chem. Soc. 1989, 111, 6578.
6. (f) Stevenson, C. D.; Sturgeon, B. E. J. Org. Chem. 1990, 55, 4090.
7. (g) Stevenson, C. D.; Halvorsen T. D.; Reiter, R. C. J. Am. Chem. Soc. 1993, 115, 12405.
8. Stevenson, C. D.; Peters, S. J.; Reidy, K. A.; Reiter, R. C. J. Org. Chem. 1992, 57, 1877.
9. (a) Katz, T. J.; Strauss, H. L. J. Chem. Phys. 1960, 32, 1873.
10. (b) Katz, T. J. J. Am. Chem. Soc. 1960, 82, 3785.
11. Strauss, H. L.; Katz, T. J.; Fraenkel, G. K. J. Am. Chem. Soc. 1963, 85, 2360.
12. Kimmel, P. L; Strauss, H. L. J. Phys. Chem. 1968, 72, 2813.
13. (e) Wenthold, P. G.; Hrovat, D. A.; Borden, W. T.; Lineberger, W. C. Science 1996, 272, 1456.
14. Hammons, J. H.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1991, 113, 4500.
15. Jahn, H. A.; Teller, E. Proc. R. Soc. London, Ser. A 1937, 161, 220.
16. Liehr, A. D. J. Phys. Chem. 1963, 67, 389.
17. (a) Boness, M. J. W.; Larkin, I. W.; Hasted, J. B.; Moore, L. Chem. Phys. Lett. 1967, 1, 292.
18. (b) Jordan, K. D.; Michejda, J. A.; Burrow, P. D. J. Am. Chem. Soc. 1976, 98, 1295.
19. (a) Schaefer, H. F., III. Theochem, in press.
20. (b) Galbraith, J. M.; Schaefer, H. F., III. J. Chem. Phys. 1996, 105, 862.
21. (c) Tschumper, G. S.; Fermann, J. T.; H. F., III. J. Chem. Phys. 1996, 104, 3676.
22. (d) King, R. A.; Galbraith, J. M.; Schaefer, H. F., III. J. Phys. Chem. 1996, 100, 6061.
23. Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
24. Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.
25. (a) Hariharan, P. C. and Pople, J. A. Theor. Chim. Acta 1973, 28, 213.
26. (b) Clark, T.; Chandrasekhar, J.; Spitznagel, G. W.; Schleyer, P. v. R. J. Comput. Chem. 1983, 4, 294.
27. See any current masthead page for ordering and Internet access instructions.
28. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T.; Petersson, G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; 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, Revision B.3; Gaussian, Inc.: Pittsburgh PA, 1995.
29. (a) Bigeleisen, J.; Mayer, M. G. J. Chem. Phys. 1947, 15, 261.
30. (b) Wolfsberg, M. Acc. Chem. Res. 1972, 5, 225.
31. Saunders, M.; Laidig, K. E.; Wolfsberg, M. J. Am. Chem. Soc. 1989, 111, 8989. We thank Professor Saunders for supplying us with a copy of this program.
32. -. (See Klimkans, A.; Larsson, S. Chem. Phys. 1994, 189, 25 and references cited therein.)
33. 2v minimum.
34. (a) Turtle, T. R.; Weissman, S. I. J. Am. Chem. Soc. 1958, 80, 5342.
35. (b) Townsend, M. G.; Weissman, S. I. J. Chem. Phys. 1960, 32, 309.
36. 1. (Lawler, R. G.; Fraenkel, G. K. J. Chem. Phys. 1968, 49, 1126.)
37. 1 does not perturb the spin densities; so all seven of the remaining protons are found to have the same hyperfine coupling constant. (Carrington, A.; Longuet-Higgins, H. C.; Moss, R. E.; Todd, P. F. Mol. Phys. 1965, 9. 187.)
38. Wentworth, W. E.; Ristau, W. J. Phys. Chem. 1969, 73, 2126.
39. Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1992, 114, 5879.
40. (a) Anet, F. A. L.; Bourn, A. J. R.; Lin, Y. S. J. Am. Chem. Soc. 1965, 86, 3576.
41. (b) Oth, J. F. M. Pure Appl. Chem. 1971, 25, 573.
42. Unrestricted (U)DFT calculations were performed for the triplet, but the triplet showed virtually no spin contamination.
43. Scaling all the (8/8)CASSCF/6-31G*vibrational frequencies by 0.9 gives K(4) = 0.36. It is generally found that ab initio vibrational frequencies require greater scaling than vibrational frequencies obtained from DFT calculations.
44. 24 is similar to that computed for ring inversion.