Theoretical Aspects of Proton Transfer Reactions in a Polar Environment

Hydrogen-Transfer Reactions

Volumn 1, Issue , 2007, Pages 303-348

  Kiefer, Philip M ^a,b   Hynes, James T ^a,b  

^a UNIVERSITY OF COLORADO   (United States)

^b ECOLE NORMALE SUPÉRIEURE   (France)

Author keywords

Adiabatic proton transfer; Hydrogen transfer reactions; Nonadiabatic 'tunneling' proton transfer; Polar environments; Theoretical aspects

Indexed keywords

EID: 34548227922     PISSN: None     EISSN: None     Source Type: Book    
DOI: 10.1002/9783527611546.ch10     Document Type: Chapter

References (168)

1. Borgis, D.; Hynes, J. T. J. Phys. Chem. 1996, 100, 1118-1128;
2. Borgis, D.; Hynes, J. T. Chem. Phys. 1993, 170, 315-346;
3. Borgis, D.; Lee, S.; Hynes, J. T. Chem. Phys. Lett. 1989, 162, 19-26;
4. Borgis, D.; Hynes, J. T. J. Chem. Phys. 1991, 94, 3619-3628;
5. Lee, S.; Hynes, J. T. J. Chim. Phys. 1996, 99, 7557-7567.
6. Ando K.; Hynes, J. T. J. Mol. Liq. 1995, 64, 25-34;
7. Ando, K.; Hynes, J. T. J. Phys. Chem. B 1997, 101, 10464-10478;
8. Ando, K.; Hynes, J. T. J Phys Chem A 1999, 103, 10398-10408;
9. Staib, A.; Borgis, D.; Hynes, J. T. J. Chem. Phys. 1995, 102, 2487-2505;
10. Ando, K.; Hynes, J. T. Faraday Discuss. 1995, 102, 435-441;
11. Ando, K.; Hynes, J. T. Adv. Chem. Phys. 1999, 110, 381-430.
12. Kiefer, P. M.; Hynes, J. T. J. Phys. Chem. A 2002, 106, 1834-1849;
13. Kiefer, P. M.; Hynes, J. T. J. Phys. Chem. A 2002, 106, 1850-1861.
14. Kiefer, P. M.; Hynes, J. T. J. Phys. Chem. A 2003, 107, 9022-9039.
15. Kiefer, P. M.; Hynes, J. T. J. Phys. Chem. A, 2004, 108, 11793-11808;
16. Kiefer, P. M.; Hynes, J. T. J. Phys. Chem. A 2004, 108, 11809-11818.
17. Timoneda, J. J.; Hynes J. T. J. Phys. Chem. 1991, 95, 10431-10442.
18. Gertner, B. J.; Hynes, J. T. Faraday Discuss. 1998, 110, 301-322.
19. Bell, R. P. The Proton in Chemistry. 2nd edn. Cornell University Press, Ithaca, NY 1973;
20. Caldin, E.; Gold, V., Proton Transfer Reactions, Chapman and Hall, London 1975;
21. Kresge, A. J. Acc. Chem. Res. 1975, 8, 354-360;
22. Hibbert, F. Adv. Phys. Org. Chem. 1986, 22, 113-212;
23. Hibbert F. Adv. Phys. Org. Chem. 1990, 26, 255-379.
24. Kreevoy, M. M.; Konasewich, D. E. Adv. Chem. Phys. 1972, 21, 243-252;
25. Kreevoy, M. M.; Oh, S-w. J. Am. Chem. Soc. 1973, 95, 4805-4810;
26. Kresge, A. J.; Silverman, D. N. Meth. Enz. 1999, 308, 276-297;
27. Kresge, A.J.; Chen, H. J.; Chiang, Y. J. Am. Chem. Soc. 1977, 99, 802-805;
28. Kresge, A.J.; Sagatys, D. S.; Chen, H. L. J. Am. Chem. Soc. 1977, 99, 7228-7233;
29. McLennan, D. J.; Wong, R. J. Aust. J. Chem. 1976, 29, 787-798;
30. Lee, I.-S.; Jeoung, E.H.; Kreevoy, M. M. J. Am. Chem. Soc. 2001, 123, 7492-7496.
31. Bell, R. P., Goodall, D. M. Proc. R. Soc. London Ser. A 1966, 294, 273-297;
32. Dixon, J. E.; Bruice, T. C. J. Am. Chem. Soc. 1970, 92, 905-909;
33. Pryor, W. A.; Kneipp, K. G. J. Am. Chem. Soc. 1971, 93 5584-5586;
34. Bell, R. P.; Cox, B. G. J. Chem. Soc. B 1971, 783-785;
35. Bordwell, F. G.; Boyle, W. J. J. Am. Chem. Soc. 1975, 97, 3447-3452.
36. Cha, Y.; Murray, C. J.; Klinman, J. P. Science 1989, 243, 1325-1330;
37. Kohen, A.; Klinman, J. P. Acc. Chem. Res. 1998, 31, 397-404;
38. Kohen, A.; Klinman, J. P. Chem. Biol. 1999, 6, R191-R198;
39. Kohen, A.; Cannio, R.; Bartolucci, S.; Klinman, J. P. Nature 1999, 399, 496-499.
40. Kresge, A. J., in Isotope Effects on Enzyme-Catalyzed Reactions, Cleland, W. W.; O'Leary, M. H.; Northrop, D. B. (Eds.), University Park Press, Baltimore, MD 1977, pp. 37-63.
41. Melander, L.; Saunders, W. H. Reaction Rates of Isotopic Molecules, Wiley, New York 1980.
42. Westheimer, F. H. Chem. Rev. 1961, 61, 265-273;
43. Melander, L. Isotope Effects on Reaction Rates, The Ronald Press Co., New York 1960.
44. Hammond, G. S. J. Am. Chem. Soc. 1955, 77, 33-338;
45. Lowry, T. H.; Richardson, K. S. Mechanism and Theory in Organic Chemistry. 3rd edn. Harper Collins, New York 1987.
46. More O'Ferral, R. A. in Proton Transfer Reactions, Caldin, E.; Gold, V. (Eds.), Chapman and Hall, London 1975, pp. 201-261.
47. Bell, R. P., The Tunnel Effect in Chemistry, Chapman and Hall, NewYork 1980;
48. Bell, R. P.; Sachs, W.H.; Tranter, R. L. Trans. Faraday Soc. 1971, 67, 1995-2003.
49. A KIE expression of the form in Eq. (10.2) neglects any mass dependence in the prefactor, the contribution of which is usually negligible, except in the case of tunneling [8, 11, 17], as well as assumes that the proton primarily resides in it ground (stretching and bending)vibrational state.
50. Marcus, R. A. J. Phys. Chem. 1968, 72, 891-899;
51. Cohen, A. O.; Marcus, R. A. J. Phys. Chem. 1968, 72, 4249-4255;
52. Marcus, R.A. J. Am. Chem. Soc. 1969, 91, 7224-7225;
53. Marcus, R. A. Faraday Symp. Chem. Soc. 1975, 10, 6068.
54. Babamov, V. K.; Marcus, R. A. J. Chem. Phys. 1981, 74, 1790-1798;
55. Hiller, C.; Manz, J.; Miller, W. H.; Römelt, J. J. Chem. Phys. 1983, 78, 3850-3856;
56. Miller, W. H. J. Am. Chem. Soc. 1979, 101, 6810-6814;
57. Skodje, R. T.; Truhlar, D. G.; Garrett, B. C. J. Chem. Phys. 1982, 77, 5955-5976;
58. Marcus, R. A.; Coltrin M. E. J. Chem. Phys. 1977, 67, 2609-2613;
59. Garrett, B. C.; Truhlar, D. G. J. Chem. Phys. 1983, 79, 4931-4938;
60. Kim, Y.; Kreevoy, M. M. J. Am. Chem. Soc. 1992, 114, 7116-7123.
61. Calculations of KIEs derived from a classical reaction path (e.g. the MEP) in the presence of a solvent or polar environment typically add quantum corrections to that path [22]. Such a reaction path, however, includes classical motion of the proton, especially near the TS, and thus this technique exhibits no difference in quantum corrections between H and D at the TS for a symmetric reaction (DGrxn=0) [22b], in contrast to the present picture. In variational TS theory for gas phase H atom transfer, the TS significantly deviates from the MEP TS and is isotope-dependent [23]. This feature has been calculated for PT in an enzyme, where the KIE has been diminished because the TS position significantly differs between H and D even in a symmetric case [22e].
62. For numerical calculations consistent with the standard view, see Alhambra, C.; Corchado, J. C.; Sanchez, M. L.; Gao, J.; Truhlar, D. G. J. Am. Chem. Soc. 2000, 122, 8197-8203;
63. Hwang, J.-K.; Warshel A. J. Phys Chem. 1993, 97, 10053-10058;
64. Hwang, J.-K.; Chu, Z. T.; Yadav, A.; Warshel, A. J. Phys. Chem. 1991, 95, 8445-8448;
65. Hwang, J.-K.; Warshel, A. J. Am. Chem. Soc. 1996, 118, 11745-11751;
66. Alhambra, C.; Gao J.; Corchado, J. C.; Villa, J.; Truhlar, D. G. J. Am. Chem. Soc. 1999, 121, 2253-2258;
67. Cui, Q.; Karplus, M. J. Am. Chem. Soc. 2002, 124, 3093-3124.
68. Garrett, B.C.; Truhlar, D. G. J. Am. Chem. Soc. 1979, 101, 4534-4547.
69. Saunders, W. H. J. Am. Chem. Soc. 1985, 107, 164-169.
70. For examples of the equilibrium solvation picture for PT in a complex system, see Bash, P. A.; Field, M. J.; Davenport, R. C.; Petsko, G. A.; Ringe, D.; Karplus, M. Biochemistry 1991, 30, 5826-5832;
71. Cui, Q.; Karplus, M. J. Am. Chem. Soc. 2001, 123, 2284-2290;
72. Alhambra, C.; Corchado, J.; Sanchez, M. L.; Garcia-Viloca, M.; Gao, J.; Truhlar, D.G. J. Phys. Chem. B 2001, 105, 11326-11340;
73. Cui, Q.; Elstner, M.; Karplus M. J. Phys. Chem. B 2002, 106, 2721-2740.
74. Dogonadze, R. R.; Kuznetzov, A. M.; Levich, V. G. Electrochim. Acta 1968, 13, 1025-1044;
75. German, E. D.; Kuznetzov, A. M.; Dogonadze, R. R. J. Chem. Soc., Faraday Trans. II 1980, 76, 1128-1146;
76. Kuznetzov, A. M. Charge Transfer in Physics, Chemistry and Biology: Physical Mechanisms of Elementary Processes and an Introduction to the Theory. Gordon and Breach, Amsterdam 1995;
77. Kuznetzov, A.M.; Ulstrup, J. Can. J. Chem. 1999, 77, 1085-1096;
78. Sühnel, J.; Gustav, K. Chem. Phys. 1984, 87, 179-187.
79. Basilevsky, M. V.; Soudackov, A.; Vener, M. V. Chem. Phys. 1995, 200, 87106;
80. Basilevsky, M. V.; Vener, M. V.; Davidovich, G. V., Soudackov, A. Chem. Phys. 1996, 208, 267-282;
81. Vener, M.V.; Rostov, I. V.; Soudackov, A.; Basilevsky, M. V. Chem. Phys. 2000, 254, 249-265.
82. Agarwal, P. K.; Billeter, S. R.; Hammes-Schiffer S. J. Phys. Chem. B 2002, 106, 3283-3293;
83. Agarwal, P. K.; Billeter, S. R.; Rajagopalan, P. T.; Benkovic, S. J.; Hammes-Schiffer, S. P. N. A S. 2002, 99, 2794-2799;
84. Hammes-Schiffer, S. Chem Phys Chem 2002, 3, 33-42;
85. Hammes-Schiffer, S.; Billeter, S. R.; Int. Rev. Phys. Chem. 2001 20, 591-616;
86. Billeter, S. R.; Webb, S. P.; Agarwal, P. K.; Iordanov T, Hammes-Schiffer S. J. Am. Chem. Soc. 2001, 123, 11262-11272;
87. Billeter, S. R.; Webb, S. P.; Iordanov, T.; Agarwal, P. K.; Hammes-Schiffer, S. J. Chem. Phys. 2001, 114, 6925-6936.
88. While these two regimes are distinctly separated, there may exist real systems where different isotopes will be in different regimes. For example, the proton potential barrier at the solvent TS configuration may be small enough such that the proton ground vibration state may be above the barrier, but still large enough such that the deuteron ground vibration state, with a smaller ZPE, may be below the barrier. The present discussion assumes that all isotopes transfer in the same regime.
89. Kim, H. J.; Hynes, J. T. J. Chem. Phys. 1992, 96, 5088-5110.
90. Kim, H. J.; Hynes, J. T. J. Am. Chem. Soc. 1992, 114, 10508-10528;
91. Kim, H. J.; Hynes, J. T. J. Amer. Chem. Soc. 1992, 114, 10528-10537.
92. Fonseca, T.; Kim, H. J.; Hynes, J. T. J. Photochem. Photobiol. A: Chem. 1994, 82, 67-79.
93. Mulliken, R. S. J. Phys. Chem. 1952, 56, 801-822;
94. Mulliken, R. S. J. Chim. Phys. 1964, 61, 20-38;
95. Mulliken, R. S.; Person, W. B. Molecular Complexes, Wiley, New York, 1969.
96. Cukier, R. I. J. Phys. Chem. 1996, 100, 15428-15443;
97. Cukier, R. I.; Nocera, D. Annu. Rev. Phys. Chem. 1998, 49, 337-369.
98. Soudackov, A.; Hammes-Schiffer, S. J. Chem. Phys. 2000, 113, 2385-2396;
99. Iordanova, N.; Decornez, H.; Hammes-Schiffer, S. J. Am. Chem. Soc. 2001, 123, 3723-3733;
100. Iordanova, N.; Hammes-Schiffer, S. J. Am. Chem. Soc. 2002, 124, 4848-4856;
101. Hammes-Schiffer, S. Acc. Chem. Res. 2001, 34, 273-281.
102. Thompson, W. H.; Hynes J. T. J. Phys. Chem. A 2001, 105, 2582-2590.
103. Marcus, R. A. J. Chem. Phys. 1956, 24, 966-978;
104. Marcus, R. A. J. Chem. Phys. 1956, 24, 979-988;
105. Marcus, R. A.; Sutin, N. Biochim. Biophys. Acta 1985, 811, 265-322;
106. Sutin, N. Prog. Inorg. Chem. 1983, 30, 441-498.
107. The recrossing correction was calculated for both ground and excited H-bond vibrational states at the transition state in Ref. [2d]. The reaction is in the adiabatic PT limit, as opposed to an earlier, more approximate treatment (Azzouz, H.; Borgis, D. J. Chem. Phys. 1993, 98, 7361-7374;
108. Azzouz, H.; Borgis, D. J. Mol. Liq. 1994, 61, 17-36), an important feature to emphasize here since this earlier treatment of the reaction has been subsequently widely used as a reference model for various calculation methods.
109. Grote, R. F.; Hynes, J.T. J. Chem. Phys. 1980, 73, 2715-2732.
110. Warshel, A. Computer Modeling of Chemical Reactions in Enzymes and Solutions, John Wiley & Sons, New York, 1991;
111. Kong, Y. S.; Warshel, A. J. Am. Chem. Soc. 1995, 117, 6234-6242;
112. Warshel, A.; Schweins, T.; Fothergil, M. J. Am. Chem. Soc. 1994, 116, 8437-8442;
113. Schweins, T.; Warshel, A. Biochemistry 1996, 35, 14232-14243;
114. Åqvist, J.; Warshel, A. Chem. Rev. 1993, 93, 2523-2544;
115. Hwang, J.-K.; King, G.; Creighton, S.; Warshel, A. J. Am. Chem. Soc. 1988, 110, 5297-5311;
116. Warshel, A.; Hwang, J.-K. Faraday Discuss. 1992, 93, 225-238.
117. Newton, M.D.; Ehrenson, S. J. Am. Chem. Soc. 1971, 93, 4971-4990;
118. Newton, M.D. J. Chem. Phys. 1977, 67, 5535-5546.
119. Agmon, N. Chem. Phys. Lett. 1995, 244, 456-462;
120. Marx, D.; Tuckerman, M. E.; Hutter, J.; Parrinello, M. Nature 1999, 397, 601-604;
121. Geissler, P. L.; Dellago, C.; Chandler, D.; Hutter, J.; Parrinello, M. Science 2001, 291, 2121-2124;
122. Schmitt, U.W.; Voth, G. A. J. Phys. Chem. B 1998, 102, 5547-5551;
123. Schmitt, U.W.; Voth, G. A. J. Chem. Phys. 1999, 111, 9361-9381;
124. Vuilleumier, R.; Borgis, D. J. Phys. Chem. B 1998, 102, 4261-4264;
125. Vuilleumier, R.; Borgis, D. J. Chem. Phys. 1999, 111, 4251-4266.
126. For a perspective on this, we refer the reader to (b). In this connection, see also (c) and (d) concerning the issue of a hydronium ion in the neighborhood of anion produced by PT.
127. Pines, E.; Pines D. in Ultrafast Hydrogen Bonding Dynamics and Proton Transfer Processes in the Condensed Phase, Elsaesser, T.; Bakker, H.J. (Eds.), Kluwer Academic, Amsterdam, 2002, 155-184;
128. Rini, M.; Magnes, B.-Z.; Pines, E.; Nibbering, E. T. J. Science 2003, 301, 349-352;
129. Mohammed, O. F.; Pines, D.; Dreyer, J.; Pines, E.; Nibbering, E. T. J. Science 2005, 310, 83-86.
130. N is defined throughout as the free energy difference between reactant and product H-bond complexes, a free energy difference that is rarely experimentally determined. The full connection to experimentally determined quantities is discussed in Ref. 43 of Ref. [4].
131. Evans, M. G.; Polanyi, M. Trans. Faraday Soc. 1936, 32, 1333-1360;
132. Evans, M. G.; Polanyi, M. Trans. Faraday Soc. 1938, 34, 11-24. The Evans-Polanyi relations were developed mainly for gas phase reactions but are also useful in solution in the context of the standard picture.
133. Swain, G. G., Stivers, E. C.; Reuwer, J. F.; Schaad, L. J. J. Am. Chem. Soc. 1958, 80, 5885-5893.
134. Kiefer, P. M.; Hynes J. T. Israel J. Chem. 2004, 44, 171-183.
135. 0 is not expected to be exactly 0.5 due to 'intrinsic' asymmetry, but the deviation from 0.5 for either H or D is not expected to be significant. For further discussion, see Ref. 45 of Ref. [4].
136. Pauling, L. J. Am. Chem. Soc. 1947, 69, 542-553.
137. Limbach, H.-H.; Pietrzak, M.; Benedict, H.; Tolstoy, P. M.; Golubev, N. S.; Denisov, G. S. J. Mol. Structure 2004, 706, 115-119;
138. Limbach, H.-H.; Pietrzak, M.; Sharif, S.; Tolstoy, P. M.; Shenderovich, I. G.; Smirnov, S. N.; Golubev, N. S.; Denisov, G. S. Chem. Eur. J. 2004 10, 5195-5204;
139. Limbach, H.-H.; Denisov, G. S.; Golubev, N. S. in Isotope Effects In Chemistry and Biology, Kohen, A.; Limbach, H.-H. (Eds.), Taylor & Francis, Boca Raton FL, 2005, Ch. 7, pp. 193-230.
140. Eisenberg, D.; Kauzman, W. The Structure and Properties of Water, Oxford University Press, New York, 1969;
141. Riddick, J. A.; Bunger, W. B. Organic Solvents: Physical Properties and Methods of Purification, 3rd edn., Wiley-Interscience, New York, 1970, pp. 67-88.
142. Shenderovich, I. G.; Burtsev, A. P.; Denisov, G. S.; Golubev, N. S.; Limbach, H. H. Magn. Reson. Chem. 2001, 39, S91-S99.
143. Siebrand, W.; Wildman, T. A; Zgierski, M. Z. J. Am. Chem. Soc. 1984, 106, 4083-4089;
144. Siebrand, W.; Wildman, T. A; Zgierski, M. Z. J. Am. Chem. Soc. 1984, 106, 4089-4096.
145. Cukier, R. I. J. Phys. Chem. B 2002, 106, 1746-1757;
146. Cukier, R. I.; Zhu, J. J Phys. Chem. B 1997, 101, 7180-7190.
147. S is analogous to the electronic diabatic solvent reorganization energy. Even though the reorganization energies and couplings are analogous, the physical picture behind the two reaction types is quite different. The reorganization energy for proton tunneling is the free energy difference associated with a Franck-Condon-like excitation (all nuclear and solvent modes other than the proton mode are held fixed) of the ground diabatic proton vibrational state at the equilibrium reactant solvent position to the ground product diabatic proton vibrational state, followed by relaxation along the solvent coordinate to the equilibrium solvent product position (See Fig. 10.13(d)).
148. Discussion of the influence of bending on these results can be found in Refs. [4] and [5a].
149. The H-bond vibrational mode is assumed to remain significantly unchanged while the reaction coordinate fluctuates from the 0-0 TS to either the 0-1 or 1-0 TS.
150. This is particularly true for H atom transfer reactions because they are weakly coupled to a polar environment, i.e. small reorganization energies (cf. H atom transfer reaction in Ref. [1e]).
151. o are obtained.
152. N and decreased Eg [5].
153. Antoniou, D.; Schwartz, S. D. P. N. A. S. 1997, 94, 12360-12365;
154. Antoniou, D.; Schwartz, S. D. J. Chem. Phys. 1999, 110, 465-472;
155. Karmacharya, R.; Schwartz, S. D. J Chem. Phys. 1999, 110, 7376-7381.
156. Further remarks on the T dependence of the Swain-Schaad ratio can be found in Section 3c of Ref. [5].
157. E. Pines, in Isotope Effects in Chemistry and Biology, Kohen, A.; Limbach, H.-H. (Eds.), Marcel Decker, Inc., New York, 2005, Ch.16, pp. 451-464.
158. The observed KIEs [9c, 9e, 63] were measured by changing the solvent from H2O to D2O, and while this change in solvent introduces other possible solvent isotope effects (i.e. viscosity), the rate limiting step in each case has been shown to be a PT step (or a series of PT steps), and thus the measured KIE corresponds to P.
159. Kim, H. J.; Staib, A.; Hynes, J. T. in Ultrafast Reaction Dynamics at Atomic-Scale Resolution Femtochemistry and Femtobiology, Nobel Symposium 101, Villy Sundstrom (Ed.), Imperial College Press, London, 1998, pp. 510-527.
160. Peters, K. S; Cashin, A.; Timbers, P. J. Am. Chem. Soc. 2000, 122, 107-113;
161. Peters, K. S; Cashin, A. J. Phys. Chem. A 2000, 104, 4833-4838;
162. Peters, K. S.; Kim, G. J. Phys. Chem. A 2001, 105, 4177-4181.
163. Andrieux, C. P.; Gamby, J.; Hapiot, P.; Saveant, J.-M. J. Am. Chem. Soc. 2003, 125, 10119-10124.
164. Tran-Thi, T.-H; Gustavsson, T.; Prayer, C.; Pommeret, S.; Hynes, J. T. Chem. Phys. Lett. 2000, 329, 421-430.
165. Tran-Thi, T.-H; Prayer, C.; Millie, P.; Uznanski, P.; Hynes, J. T. J. Phys. Chem. A 2002, 106, 2244-2255.
166. Hynes, J. T.; Tran-Thi, T.-H; Granucci, G. J. Photochem. Photobiol.; A. Photochemistry 2002, 154, 3-11.
167. Granucci, G.; Hynes, J. T.; Millie, P.; Tran-Thi, T.-H. J. Am. Chem. Soc. 2000, 122, 12235-12245.
168. Elsaesser, T. in Ultrafast Hydrogen Bonding Dynamics and Proton Transfer Processes in the Condensed Phase, Elsaesser, T.; Bakker, H.J. (Eds.), Kluwer Academic, Amsterdam, 2002, pp. 119-153.