Model calculations of isotope effects using structures containing low-barrier hydrogen bonds

Journal of the American Chemical Society

Volumn 118, Issue 7, 1996, Pages 1663-1668

  Huskey, W Phillip ^a  

^a RUTGERS UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ARTICLE; DRUG STRUCTURE; HYDROGEN BOND; ISOTOPE LABELING; MATHEMATICAL MODEL; THERMODYNAMICS;

EID: 0029971658     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9529246     Document Type: Article

References (66)

1. (a) Kreevoy, M. M., Liang, T. M.; Chang, K. C. J. Am. Chem. Soc. 1977, 99, 5207-5209.
2. (b) Kreevoy, M. M.; Liang, T. M. J Am. Chem. Soc. 1980, 102, 3315-3322.
3. Hibbert, F.; Emsley, J. Adv. Phys. Org. Chem. 1990, 26, 255-379.
4. Cleland. W. W. Biochemistry 1992, 31, 317-319.
5. Kreevoy, M. M.; Cleland, W. W. Science 1994, 264, 1887-1890.
6. Schemer, S.; Kar, T. J. Am. Chem. Soc 1995, 117, 6970-6975. Warshel, A.; Papazyan, A.; Kollman, P. A. Science 1995, 269, 102-103. Cleland, W. W., Kreevoy, M. M. Science 1995, 269, 104, Frey, P. A. Science 1995, 269, 104-106.
7. Schemer, S.; Kar, T. J. Am. Chem. Soc 1995, 117, 6970-6975. Warshel, A.; Papazyan, A.; Kollman, P. A. Science 1995, 269, 102-103. Cleland, W. W., Kreevoy, M. M. Science 1995, 269, 104, Frey, P. A. Science 1995, 269, 104-106.
8. Schemer, S.; Kar, T. J. Am. Chem. Soc 1995, 117, 6970-6975. Warshel, A.; Papazyan, A.; Kollman, P. A. Science 1995, 269, 102-103. Cleland, W. W., Kreevoy, M. M. Science 1995, 269, 104, Frey, P. A. Science 1995, 269, 104-106.
9. Schemer, S.; Kar, T. J. Am. Chem. Soc 1995, 117, 6970-6975. Warshel, A.; Papazyan, A.; Kollman, P. A. Science 1995, 269, 102-103. Cleland, W. W., Kreevoy, M. M. Science 1995, 269, 104, Frey, P. A. Science 1995, 269, 104-106.
10. Swain, C. G., Kuhn, D. A.; Schowen, R. L J Am. Chem. Soc. 1965, 87, 1553-1561, Cordes, E. H. Prog. Phys. Org. Chem. 1967, 4, 1-44, Schowen, R. L. Prog. Phys. Org. Chem. 1972, 9, 275-331.
11. Swain, C. G., Kuhn, D. A.; Schowen, R. L J Am. Chem. Soc. 1965, 87, 1553-1561, Cordes, E. H. Prog. Phys. Org. Chem. 1967, 4, 1-44, Schowen, R. L. Prog. Phys. Org. Chem. 1972, 9, 275-331.
12. Swain, C. G., Kuhn, D. A.; Schowen, R. L J Am. Chem. Soc. 1965, 87, 1553-1561, Cordes, E. H. Prog. Phys. Org. Chem. 1967, 4, 1-44, Schowen, R. L. Prog. Phys. Org. Chem. 1972, 9, 275-331.
13. Minor, S. S.; Schowen, R. L J. Am. Chem. Soc. 1973, 95, 2279-2281 Young, P. R., Jencks, W. P J Am Chem. Soc 1978, 100, 1228-1235. Eliason, R.; Kreevoy, M. M J. Am. Chem. Soc. 1978, 100, 7037-7041. Hegazi, M.; Mata-Segreda, J. F., Schowen, R. L. J. Org. Chem. 1980, 45, 307-310. Schowen, R. L. Mol. Struct. Energ. 1988, 9, 119-168 (Mechanistic Principles of Enzyme Activity: Liebman, J. F., Greenberg, A., Eds.) Gandour, R. D.; Nabulsi, N A. R.; Fonczek, F. R. J. Am. Chem. Soc. 1990, 112, 7817-7819
14. Minor, S. S.; Schowen, R. L J. Am. Chem. Soc. 1973, 95, 2279-2281 Young, P. R., Jencks, W. P J Am Chem. Soc 1978, 100, 1228-1235. Eliason, R.; Kreevoy, M. M J. Am. Chem. Soc. 1978, 100, 7037-7041. Hegazi, M.; Mata-Segreda, J. F., Schowen, R. L. J. Org. Chem. 1980, 45, 307-310. Schowen, R. L. Mol. Struct. Energ. 1988, 9, 119-168 (Mechanistic Principles of Enzyme Activity: Liebman, J. F., Greenberg, A., Eds.) Gandour, R. D.; Nabulsi, N A. R.; Fonczek, F. R. J. Am. Chem. Soc. 1990, 112, 7817-7819
15. Minor, S. S.; Schowen, R. L J. Am. Chem. Soc. 1973, 95, 2279-2281 Young, P. R., Jencks, W. P J Am Chem. Soc 1978, 100, 1228-1235. Eliason, R.; Kreevoy, M. M J. Am. Chem. Soc. 1978, 100, 7037-7041. Hegazi, M.; Mata-Segreda, J. F., Schowen, R. L. J. Org. Chem. 1980, 45, 307-310. Schowen, R. L. Mol. Struct. Energ. 1988, 9, 119-168 (Mechanistic Principles of Enzyme Activity: Liebman, J. F., Greenberg, A., Eds.) Gandour, R. D.; Nabulsi, N A. R.; Fonczek, F. R. J. Am. Chem. Soc. 1990, 112, 7817-7819
16. Minor, S. S.; Schowen, R. L J. Am. Chem. Soc. 1973, 95, 2279-2281 Young, P. R., Jencks, W. P J Am Chem. Soc 1978, 100, 1228-1235. Eliason, R.; Kreevoy, M. M J. Am. Chem. Soc. 1978, 100, 7037-7041. Hegazi, M.; Mata-Segreda, J. F., Schowen, R. L. J. Org. Chem. 1980, 45, 307-310. Schowen, R. L. Mol. Struct. Energ. 1988, 9, 119-168 (Mechanistic Principles of Enzyme Activity: Liebman, J. F., Greenberg, A., Eds.) Gandour, R. D.; Nabulsi, N A. R.; Fonczek, F. R. J. Am. Chem. Soc. 1990, 112, 7817-7819
17. Minor, S. S.; Schowen, R. L J. Am. Chem. Soc. 1973, 95, 2279-2281 Young, P. R., Jencks, W. P J Am Chem. Soc 1978, 100, 1228-1235. Eliason, R.; Kreevoy, M. M J. Am. Chem. Soc. 1978, 100, 7037-7041. Hegazi, M.; Mata-Segreda, J. F., Schowen, R. L. J. Org. Chem. 1980, 45, 307-310. Schowen, R. L. Mol. Struct. Energ. 1988, 9, 119-168 (Mechanistic Principles of Enzyme Activity: Liebman, J. F., Greenberg, A., Eds.) Gandour, R. D.; Nabulsi, N A. R.; Fonczek, F. R. J. Am. Chem. Soc. 1990, 112, 7817-7819
18. Minor, S. S.; Schowen, R. L J. Am. Chem. Soc. 1973, 95, 2279-2281 Young, P. R., Jencks, W. P J Am Chem. Soc 1978, 100, 1228-1235. Eliason, R.; Kreevoy, M. M J. Am. Chem. Soc. 1978, 100, 7037-7041. Hegazi, M.; Mata-Segreda, J. F., Schowen, R. L. J. Org. Chem. 1980, 45, 307-310. Schowen, R. L. Mol. Struct. Energ. 1988, 9, 119-168 (Mechanistic Principles of Enzyme Activity: Liebman, J. F., Greenberg, A., Eds.) Gandour, R. D.; Nabulsi, N A. R.; Fonczek, F. R. J. Am. Chem. Soc. 1990, 112, 7817-7819
19. Minor, S. S.; Schowen, R. L J. Am. Chem. Soc. 1973, 95, 2279-2281 Young, P. R., Jencks, W. P J Am Chem. Soc 1978, 100, 1228-1235. Eliason, R.; Kreevoy, M. M J. Am. Chem. Soc. 1978, 100, 7037-7041. Hegazi, M.; Mata-Segreda, J. F., Schowen, R. L. J. Org. Chem. 1980, 45, 307-310. Schowen, R. L. Mol. Struct. Energ. 1988, 9, 119-168 (Mechanistic Principles of Enzyme Activity: Liebman, J. F., Greenberg, A., Eds.) Gandour, R. D.; Nabulsi, N A. R.; Fonczek, F. R. J. Am. Chem. Soc. 1990, 112, 7817-7819
20. -1.
21. Perrin, C. L. Science 1994, 266, 1665-1668. Perrin, C. L.; Thoburn, J. D. J. Am. Chem. Soc. 1992, 114, 8559-8565. Perrin, C. L , Thoburn, J. D. J. Am. Chem. Soc. 1989, 111, 8010-8012. Frey, P. A., Whitt, S. A.; Tobin, J. B. Science 1994, 264, 1927-1930. Golubev, N. S., Smirnov, S. N.; Gindin, V. A.; Denisov, G. S.; Benedict, H., Limbach, H.-H. J. Am. Chem. Soc. 1994, 116, 12055-12056 Tong, H.; Davis, L. Biochemistry 1995, 34, 3362-3367. Tobin, J B., Whitt, S. A.; Cassidy, C. S.; Frey, P. A. Biochemistry 1995, 34, 6919-6924.
22. Perrin, C. L. Science 1994, 266, 1665-1668. Perrin, C. L.; Thoburn, J. D. J. Am. Chem. Soc. 1992, 114, 8559-8565. Perrin, C. L , Thoburn, J. D. J. Am. Chem. Soc. 1989, 111, 8010-8012. Frey, P. A., Whitt, S. A.; Tobin, J. B. Science 1994, 264, 1927-1930. Golubev, N. S., Smirnov, S. N.; Gindin, V. A.; Denisov, G. S.; Benedict, H., Limbach, H.-H. J. Am. Chem. Soc. 1994, 116, 12055-12056 Tong, H.; Davis, L. Biochemistry 1995, 34, 3362-3367. Tobin, J B., Whitt, S. A.; Cassidy, C. S.; Frey, P. A. Biochemistry 1995, 34, 6919-6924.
23. Perrin, C. L. Science 1994, 266, 1665-1668. Perrin, C. L.; Thoburn, J. D. J. Am. Chem. Soc. 1992, 114, 8559-8565. Perrin, C. L , Thoburn, J. D. J. Am. Chem. Soc. 1989, 111, 8010-8012. Frey, P. A., Whitt, S. A.; Tobin, J. B. Science 1994, 264, 1927-1930. Golubev, N. S., Smirnov, S. N.; Gindin, V. A.; Denisov, G. S.; Benedict, H., Limbach, H.-H. J. Am. Chem. Soc. 1994, 116, 12055-12056 Tong, H.; Davis, L. Biochemistry 1995, 34, 3362-3367. Tobin, J B., Whitt, S. A.; Cassidy, C. S.; Frey, P. A. Biochemistry 1995, 34, 6919-6924.
24. Perrin, C. L. Science 1994, 266, 1665-1668. Perrin, C. L.; Thoburn, J. D. J. Am. Chem. Soc. 1992, 114, 8559-8565. Perrin, C. L , Thoburn, J. D. J. Am. Chem. Soc. 1989, 111, 8010-8012. Frey, P. A., Whitt, S. A.; Tobin, J. B. Science 1994, 264, 1927-1930. Golubev, N. S., Smirnov, S. N.; Gindin, V. A.; Denisov, G. S.; Benedict, H., Limbach, H.-H. J. Am. Chem. Soc. 1994, 116, 12055-12056 Tong, H.; Davis, L. Biochemistry 1995, 34, 3362-3367. Tobin, J B., Whitt, S. A.; Cassidy, C. S.; Frey, P. A. Biochemistry 1995, 34, 6919-6924.
25. Perrin, C. L. Science 1994, 266, 1665-1668. Perrin, C. L.; Thoburn, J. D. J. Am. Chem. Soc. 1992, 114, 8559-8565. Perrin, C. L , Thoburn, J. D. J. Am. Chem. Soc. 1989, 111, 8010-8012. Frey, P. A., Whitt, S. A.; Tobin, J. B. Science 1994, 264, 1927-1930. Golubev, N. S., Smirnov, S. N.; Gindin, V. A.; Denisov, G. S.; Benedict, H., Limbach, H.-H. J. Am. Chem. Soc. 1994, 116, 12055-12056 Tong, H.; Davis, L. Biochemistry 1995, 34, 3362-3367. Tobin, J B., Whitt, S. A.; Cassidy, C. S.; Frey, P. A. Biochemistry 1995, 34, 6919-6924.
26. Perrin, C. L. Science 1994, 266, 1665-1668. Perrin, C. L.; Thoburn, J. D. J. Am. Chem. Soc. 1992, 114, 8559-8565. Perrin, C. L , Thoburn, J. D. J. Am. Chem. Soc. 1989, 111, 8010-8012. Frey, P. A., Whitt, S. A.; Tobin, J. B. Science 1994, 264, 1927-1930. Golubev, N. S., Smirnov, S. N.; Gindin, V. A.; Denisov, G. S.; Benedict, H., Limbach, H.-H. J. Am. Chem. Soc. 1994, 116, 12055-12056 Tong, H.; Davis, L. Biochemistry 1995, 34, 3362-3367. Tobin, J B., Whitt, S. A.; Cassidy, C. S.; Frey, P. A. Biochemistry 1995, 34, 6919-6924.
27. Perrin, C. L. Science 1994, 266, 1665-1668. Perrin, C. L.; Thoburn, J. D. J. Am. Chem. Soc. 1992, 114, 8559-8565. Perrin, C. L , Thoburn, J. D. J. Am. Chem. Soc. 1989, 111, 8010-8012. Frey, P. A., Whitt, S. A.; Tobin, J. B. Science 1994, 264, 1927-1930. Golubev, N. S., Smirnov, S. N.; Gindin, V. A.; Denisov, G. S.; Benedict, H., Limbach, H.-H. J. Am. Chem. Soc. 1994, 116, 12055-12056 Tong, H.; Davis, L. Biochemistry 1995, 34, 3362-3367. Tobin, J B., Whitt, S. A.; Cassidy, C. S.; Frey, P. A. Biochemistry 1995, 34, 6919-6924.
28. Emsley, J., Gold, V . Szeto, W. T. A. J. Chem. Soc., Dalton Trans. 1986, 2641-2644. Hibdon, S. A.; Coleman, C. A., Wang, J.; Murray, C. J Bioorg. Chem. 1992, 20, 334-344. Loh, S . Markley, J. L. Biochemistry 1994, 33, 1029-1036 Arrowsmith, C. H., Guo, H X , Kresge, A. J. J. Am. Chem. Soc 1994, 116, 8890-8894. Kresge, A J : More O'Ferrall, R. A , Powel, M. F. In Isotopes in Organic Chemistry, Buncel, E., Lee, C C., Eds., Elsevier. Amsterdam. 1987; Vol. 7, Chapter 4.
29. Emsley, J., Gold, V . Szeto, W. T. A. J. Chem. Soc., Dalton Trans. 1986, 2641-2644. Hibdon, S. A.; Coleman, C. A., Wang, J.; Murray, C. J Bioorg. Chem. 1992, 20, 334-344. Loh, S . Markley, J. L. Biochemistry 1994, 33, 1029-1036 Arrowsmith, C. H., Guo, H X , Kresge, A. J. J. Am. Chem. Soc 1994, 116, 8890-8894. Kresge, A J : More O'Ferrall, R. A , Powel, M. F. In Isotopes in Organic Chemistry, Buncel, E., Lee, C C., Eds., Elsevier. Amsterdam. 1987; Vol. 7, Chapter 4.
30. Emsley, J., Gold, V . Szeto, W. T. A. J. Chem. Soc., Dalton Trans. 1986, 2641-2644. Hibdon, S. A.; Coleman, C. A., Wang, J.; Murray, C. J Bioorg. Chem. 1992, 20, 334-344. Loh, S . Markley, J. L. Biochemistry 1994, 33, 1029-1036 Arrowsmith, C. H., Guo, H X , Kresge, A. J. J. Am. Chem. Soc 1994, 116, 8890-8894. Kresge, A J : More O'Ferrall, R. A , Powel, M. F. In Isotopes in Organic Chemistry, Buncel, E., Lee, C C., Eds., Elsevier. Amsterdam. 1987; Vol. 7, Chapter 4.
31. Emsley, J., Gold, V . Szeto, W. T. A. J. Chem. Soc., Dalton Trans. 1986, 2641-2644. Hibdon, S. A.; Coleman, C. A., Wang, J.; Murray, C. J Bioorg. Chem. 1992, 20, 334-344. Loh, S . Markley, J. L. Biochemistry 1994, 33, 1029-1036 Arrowsmith, C. H., Guo, H X , Kresge, A. J. J. Am. Chem. Soc 1994, 116, 8890-8894. Kresge, A J : More O'Ferrall, R. A , Powel, M. F. In Isotopes in Organic Chemistry, Buncel, E., Lee, C C., Eds., Elsevier. Amsterdam. 1987; Vol. 7, Chapter 4.
32. Emsley, J., Gold, V . Szeto, W. T. A. J. Chem. Soc., Dalton Trans. 1986, 2641-2644. Hibdon, S. A.; Coleman, C. A., Wang, J.; Murray, C. J Bioorg. Chem. 1992, 20, 334-344. Loh, S . Markley, J. L. Biochemistry 1994, 33, 1029-1036 Arrowsmith, C. H., Guo, H X , Kresge, A. J. J. Am. Chem. Soc 1994, 116, 8890-8894. Kresge, A J : More O'Ferrall, R. A , Powel, M. F. In Isotopes in Organic Chemistry, Buncel, E., Lee, C C., Eds., Elsevier. Amsterdam. 1987; Vol. 7, Chapter 4.
33. Bigeleisen, J.; Goeppert-Mayer, M. J. Chern. Phys. 1947, 15, 261 - 267. Wolfsberg, M.; Stern, M. J. Pure Appl Chem. 1964, 8, 225-242.
34. Bigeleisen, J.; Goeppert-Mayer, M. J. Chern. Phys. 1947, 15, 261 - 267. Wolfsberg, M.; Stern, M. J. Pure Appl Chem. 1964, 8, 225-242.
35. Several procedures could be used to calculate of vibrational partition functions for polyatomic molecules with anharmonic potentials. (Some examples include: Bowman, J. M. J. Chem. Phys. 1978, 68, 608-610. Alvarez-Collado, J. R.; Buenker, R. J. J. Comput. Chem. 1992, 13, 135-141. Maessen, B.; Wolfsberg, M. J. Chem Phys. 1984, 80, 4651-4662. Martin, J. M L.; Francois, J. P., Gijbels, R. J. Chem. Phys. 1992, 96, 7633-7645. Isaacson, A. D., Truhlar, D. G. J. Chem. Phys. 1984, 80, 2888-2896. Topper, R. Q.; Zhang, Q.; Liu, Y. P.; Truhlar, D. G. J. Chem. Phys. 1993, 98, 4991-5005. Galloy, C.; Lorquet, J. C. Chem. Phys. Lett. 1982, 93, 26-30). The method used here assumes that the partition function for one normal-mode (and harmonic) vibration can be replaced with a partition function for a vibrational potential defined by eq 1.
36. Several procedures could be used to calculate of vibrational partition functions for polyatomic molecules with anharmonic potentials. (Some examples include: Bowman, J. M. J. Chem. Phys. 1978, 68, 608-610. Alvarez-Collado, J. R.; Buenker, R. J. J. Comput. Chem. 1992, 13, 135-141. Maessen, B.; Wolfsberg, M. J. Chem Phys. 1984, 80, 4651-4662. Martin, J. M L.; Francois, J. P., Gijbels, R. J. Chem. Phys. 1992, 96, 7633-7645. Isaacson, A. D., Truhlar, D. G. J. Chem. Phys. 1984, 80, 2888-2896. Topper, R. Q.; Zhang, Q.; Liu, Y. P.; Truhlar, D. G. J. Chem. Phys. 1993, 98, 4991-5005. Galloy, C.; Lorquet, J. C. Chem. Phys. Lett. 1982, 93, 26-30). The method used here assumes that the partition function for one normal-mode (and harmonic) vibration can be replaced with a partition function for a vibrational potential defined by eq 1.
37. Several procedures could be used to calculate of vibrational partition functions for polyatomic molecules with anharmonic potentials. (Some examples include: Bowman, J. M. J. Chem. Phys. 1978, 68, 608-610. Alvarez-Collado, J. R.; Buenker, R. J. J. Comput. Chem. 1992, 13, 135-141. Maessen, B.; Wolfsberg, M. J. Chem Phys. 1984, 80, 4651-4662. Martin, J. M L.; Francois, J. P., Gijbels, R. J. Chem. Phys. 1992, 96, 7633-7645. Isaacson, A. D., Truhlar, D. G. J. Chem. Phys. 1984, 80, 2888-2896. Topper, R. Q.; Zhang, Q.; Liu, Y. P.; Truhlar, D. G. J. Chem. Phys. 1993, 98, 4991-5005. Galloy, C.; Lorquet, J. C. Chem. Phys. Lett. 1982, 93, 26-30). The method used here assumes that the partition function for one normal-mode (and harmonic) vibration can be replaced with a partition function for a vibrational potential defined by eq 1.
38. Several procedures could be used to calculate of vibrational partition functions for polyatomic molecules with anharmonic potentials. (Some examples include: Bowman, J. M. J. Chem. Phys. 1978, 68, 608-610. Alvarez-Collado, J. R.; Buenker, R. J. J. Comput. Chem. 1992, 13, 135-141. Maessen, B.; Wolfsberg, M. J. Chem Phys. 1984, 80, 4651-4662. Martin, J. M L.; Francois, J. P., Gijbels, R. J. Chem. Phys. 1992, 96, 7633-7645. Isaacson, A. D., Truhlar, D. G. J. Chem. Phys. 1984, 80, 2888-2896. Topper, R. Q.; Zhang, Q.; Liu, Y. P.; Truhlar, D. G. J. Chem. Phys. 1993, 98, 4991-5005. Galloy, C.; Lorquet, J. C. Chem. Phys. Lett. 1982, 93, 26-30). The method used here assumes that the partition function for one normal-mode (and harmonic) vibration can be replaced with a partition function for a vibrational potential defined by eq 1.
39. Several procedures could be used to calculate of vibrational partition functions for polyatomic molecules with anharmonic potentials. (Some examples include: Bowman, J. M. J. Chem. Phys. 1978, 68, 608-610. Alvarez-Collado, J. R.; Buenker, R. J. J. Comput. Chem. 1992, 13, 135-141. Maessen, B.; Wolfsberg, M. J. Chem Phys. 1984, 80, 4651-4662. Martin, J. M L.; Francois, J. P., Gijbels, R. J. Chem. Phys. 1992, 96, 7633-7645. Isaacson, A. D., Truhlar, D. G. J. Chem. Phys. 1984, 80, 2888-2896. Topper, R. Q.; Zhang, Q.; Liu, Y. P.; Truhlar, D. G. J. Chem. Phys. 1993, 98, 4991-5005. Galloy, C.; Lorquet, J. C. Chem. Phys. Lett. 1982, 93, 26-30). The method used here assumes that the partition function for one normal-mode (and harmonic) vibration can be replaced with a partition function for a vibrational potential defined by eq 1.
40. Several procedures could be used to calculate of vibrational partition functions for polyatomic molecules with anharmonic potentials. (Some examples include: Bowman, J. M. J. Chem. Phys. 1978, 68, 608-610. Alvarez-Collado, J. R.; Buenker, R. J. J. Comput. Chem. 1992, 13, 135-141. Maessen, B.; Wolfsberg, M. J. Chem Phys. 1984, 80, 4651-4662. Martin, J. M L.; Francois, J. P., Gijbels, R. J. Chem. Phys. 1992, 96, 7633-7645. Isaacson, A. D., Truhlar, D. G. J. Chem. Phys. 1984, 80, 2888-2896. Topper, R. Q.; Zhang, Q.; Liu, Y. P.; Truhlar, D. G. J. Chem. Phys. 1993, 98, 4991-5005. Galloy, C.; Lorquet, J. C. Chem. Phys. Lett. 1982, 93, 26-30). The method used here assumes that the partition function for one normal-mode (and harmonic) vibration can be replaced with a partition function for a vibrational potential defined by eq 1.
41. Several procedures could be used to calculate of vibrational partition functions for polyatomic molecules with anharmonic potentials. (Some examples include: Bowman, J. M. J. Chem. Phys. 1978, 68, 608-610. Alvarez-Collado, J. R.; Buenker, R. J. J. Comput. Chem. 1992, 13, 135-141. Maessen, B.; Wolfsberg, M. J. Chem Phys. 1984, 80, 4651-4662. Martin, J. M L.; Francois, J. P., Gijbels, R. J. Chem. Phys. 1992, 96, 7633-7645. Isaacson, A. D., Truhlar, D. G. J. Chem. Phys. 1984, 80, 2888-2896. Topper, R. Q.; Zhang, Q.; Liu, Y. P.; Truhlar, D. G. J. Chem. Phys. 1993, 98, 4991-5005. Galloy, C.; Lorquet, J. C. Chem. Phys. Lett. 1982, 93, 26-30). The method used here assumes that the partition function for one normal-mode (and harmonic) vibration can be replaced with a partition function for a vibrational potential defined by eq 1.
42. (a) Melander, L.; Saunders, W. H., Jr. Reaction Rates of Isotopic Molecules: Wiley: New York, 1980.
43. (b) Sims, L. B., Lewis, D. E. Isotopes in Organic Chemistry, Buncel, E , Lee, C. C., Eds.; Elsevier: New York, 1984: Vol. 6. pp 161-259.
44. (c) Buddenbaum, W. E.; Shiner, V. J., Jr. In Isotope Effects on Enzyme Catalyzed Reactions: Cleland, W. W., O'Leary, M. H., Northrop, D. R . Eds.; University Park Press: Baltimore, 1977; pp 1 -36.
45. (d) Huskey, W. P. In Enzyme Mechanism from Isotope Effects: Cook, P F . Ed., CRC Press; Boca Raton. FL. 1991: Chapter 2.
46. Timidei, A.; Zerbi, G. Naturforschung 1970, 25, 1729-1731 Serrallach, A.; Meyer, R.; Gunthard, H. H. J. Mol. Spectrosc. 1974, 52, 94-129.
47. Timidei, A.; Zerbi, G. Naturforschung 1970, 25, 1729-1731 Serrallach, A.; Meyer, R.; Gunthard, H. H. J. Mol. Spectrosc. 1974, 52, 94-129.
48. Badger, R. M. J. Chem. Phys. 1935, 3, 710-714.
49. Hertzberg, G. Molecular Spectra and Molecular Structure II. Infrared and Raman Spectra of Polyatomic Molecules, D. Van Nostrand, Inc., Princeton. NJ, 1945; p 172.
50. Gwinn, W. D. J. Chem. Phys 1971, 55, 477-481.
51. Heilbronner, E.; Rtishauser, H.; Gerson, F. Helv. Chim. Acta 1959, 42, 2285-2303. Chan, S. I., Stelman, D. J. Mol. Spectrosc. 1963, 10, 278-299. Chan, S. I.; Stelman, D.; Thompson, L. E J. Chem. Phys. 1964, 41, 2828-2835.
52. Heilbronner, E.; Rtishauser, H.; Gerson, F. Helv. Chim. Acta 1959, 42, 2285-2303. Chan, S. I., Stelman, D. J. Mol. Spectrosc. 1963, 10, 278-299. Chan, S. I.; Stelman, D.; Thompson, L. E J. Chem. Phys. 1964, 41, 2828-2835.
53. Heilbronner, E.; Rtishauser, H.; Gerson, F. Helv. Chim. Acta 1959, 42, 2285-2303. Chan, S. I., Stelman, D. J. Mol. Spectrosc. 1963, 10, 278-299. Chan, S. I.; Stelman, D.; Thompson, L. E J. Chem. Phys. 1964, 41, 2828-2835.
54. (a) Wilson, E. B., Jr.; Decius, J. C.; Cross, P. C. Molecular Vibrations. The Theory of Infrared and Raman Vibrational Spectra: McGraw-Hill Book Company: New York, 1955 (Dover edition, 1980)
55. (b) Reference 19a, Appendix III.
56. mc). where M is a diagonal matrix containing inverse square roots of atomic masses).
57. Westheimer, F. H. Chem. Rev. 1961, I, 265-273. Bigeleisen, J Pure Appl. Chem. 1964, 8, 217-233.
58. Westheimer, F. H. Chem. Rev. 1961, I, 265-273. Bigeleisen, J Pure Appl. Chem. 1964, 8, 217-233.
59. D presented here.
60. It is worth recalling that unusual temperature effects in kinetic isotope effect studies sometimes arise from temperature-induced changes in mechanism or changes in rate-limiting step or from reaction-coordinate tunneling. Complete elimination of these possible interpretations would be challenging.
61. (a) Bergman, N. Å.; Chiang, Y.; Kresge, A. J. J. Am. Chem. Soc. 1978, 100, 5954-5956.
62. (b) Yang, C. C.; Jencks. W P. J. Am. Chem. Soc. 1988, 110, 1972-2973.
63. (c) Fisher, H.; DeCandis, F X.; Ogden, S. D.; Jencks, W. P. J. Am. Chem. Soc. 1980, 102, 1340-1347.
64. (d) Cox, M. M.; Jencks, W P J. Am. Chem, Soc. 1978, 100, 5956-5957
65. (e) Cox, M M.; Jencks, W. P. J Am. Chem. Soc. 1981, 103, 572-580.
66. 21 tends to become independent of the coupling strength and modest changes in structure