Theory of rates of SN2 reactions and relation to those of outer sphere bond rupture electron transfers

Journal of Physical Chemistry A

Volumn 101, Issue 22, 1997, Pages 4072-4087

  Marcus, R A ^a  

^a CALIFORNIA INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001726244     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp963722e     Document Type: Article

References (109)

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3. (b) More recent analyses are given in: Eberson, L.; Shaik, S. J. Am. Chem. Soc. 1990, 112, 4484. Eberson, L. New J. Chem. 1992, 16, 151.
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26. Lewis, E. S. J. Am. Chem. Soc. 1989, 111, 7576. Lewis, E. S. J. Phys. Org. Chem. 1990, 3, 1. Lewis, E. S.; Douglas, T. A.; McLaughlin, M. L. Adv. Chem. Ser. 1987, 215, 35. Lewis, E. S. J. Am. Chem. Soc. 1985, 107, 6668. Niyazymbetov, M. E.; Zhou, R. F.; Evans, D. H. J. Chem. Soc., Perkins Trans. 2 1996, 1957. Cf. Lewis, E. S. J. Phys. Chem. 1986, 90, 3756. Lewis, E. S.; Hu, D. D. J. Am. Chem. Soc. 1984, 106, 3292.
27. Lewis, E. S. J. Am. Chem. Soc. 1989, 111, 7576. Lewis, E. S. J. Phys. Org. Chem. 1990, 3, 1. Lewis, E. S.; Douglas, T. A.; McLaughlin, M. L. Adv. Chem. Ser. 1987, 215, 35. Lewis, E. S. J. Am. Chem. Soc. 1985, 107, 6668. Niyazymbetov, M. E.; Zhou, R. F.; Evans, D. H. J. Chem. Soc., Perkins Trans. 2 1996, 1957. Cf. Lewis, E. S. J. Phys. Chem. 1986, 90, 3756. Lewis, E. S.; Hu, D. D. J. Am. Chem. Soc. 1984, 106, 3292.
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32. i there.
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39. (a) For example: Marcus, R. A.; Sutin, N. Biochim. Biophys. Acta 1985, 811, 265; Comments Inorg. Chem. 1986, 5, 119.
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42. For example: Wladkowski, B. D.; Brauman, J. I. J. Phys. Chem. 1993, 97, 13158. Pellerite, M. J.; Brauman, J. I. J. Am. Chem. Soc. 1983, 105, 2672; J. Am. Chem. Soc. 1980, 102, 5993. Dodd, J. A.; Brauman, J. I. J. Am. Chem. Soc. 1984, 106, 5356. Dodd, J. A.; Brauman, J. I. J. Phys. Chem. 1986, 90, 3559. Staneke, P. O.; Groothuis, G.; Ingemann, S.; Nibbering, N. M. M. J. Phys. Org. Chem. 1996, 9, 471. De Puy, C. H.; Gronert, S.; Mullin, A.; Bierbaum, V. M. J. Am. Chem. Soc. 1990, 112, 8650. Barlow, S. E.; Van Doren, J. M.; Bierbaum, V. M. J. Am. Chem. Soc. 1988, 110, 7240. As pointed out by Brauman and co-workers, the calculations of the gas phase reaction barriers from the experimental data take into account the multiple transition states.
43. For example: Wladkowski, B. D.; Brauman, J. I. J. Phys. Chem. 1993, 97, 13158. Pellerite, M. J.; Brauman, J. I. J. Am. Chem. Soc. 1983, 105, 2672; J. Am. Chem. Soc. 1980, 102, 5993. Dodd, J. A.; Brauman, J. I. J. Am. Chem. Soc. 1984, 106, 5356. Dodd, J. A.; Brauman, J. I. J. Phys. Chem. 1986, 90, 3559. Staneke, P. O.; Groothuis, G.; Ingemann, S.; Nibbering, N. M. M. J. Phys. Org. Chem. 1996, 9, 471. De Puy, C. H.; Gronert, S.; Mullin, A.; Bierbaum, V. M. J. Am. Chem. Soc. 1990, 112, 8650. Barlow, S. E.; Van Doren, J. M.; Bierbaum, V. M. J. Am. Chem. Soc. 1988, 110, 7240. As pointed out by Brauman and co-workers, the calculations of the gas phase reaction barriers from the experimental data take into account the multiple transition states.
44. For example: Wladkowski, B. D.; Brauman, J. I. J. Phys. Chem. 1993, 97, 13158. Pellerite, M. J.; Brauman, J. I. J. Am. Chem. Soc. 1983, 105, 2672; J. Am. Chem. Soc. 1980, 102, 5993. Dodd, J. A.; Brauman, J. I. J. Am. Chem. Soc. 1984, 106, 5356. Dodd, J. A.; Brauman, J. I. J. Phys. Chem. 1986, 90, 3559. Staneke, P. O.; Groothuis, G.; Ingemann, S.; Nibbering, N. M. M. J. Phys. Org. Chem. 1996, 9, 471. De Puy, C. H.; Gronert, S.; Mullin, A.; Bierbaum, V. M. J. Am. Chem. Soc. 1990, 112, 8650. Barlow, S. E.; Van Doren, J. M.; Bierbaum, V. M. J. Am. Chem. Soc. 1988, 110, 7240. As pointed out by Brauman and co-workers, the calculations of the gas phase reaction barriers from the experimental data take into account the multiple transition states.
45. For example: Wladkowski, B. D.; Brauman, J. I. J. Phys. Chem. 1993, 97, 13158. Pellerite, M. J.; Brauman, J. I. J. Am. Chem. Soc. 1983, 105, 2672; J. Am. Chem. Soc. 1980, 102, 5993. Dodd, J. A.; Brauman, J. I. J. Am. Chem. Soc. 1984, 106, 5356. Dodd, J. A.; Brauman, J. I. J. Phys. Chem. 1986, 90, 3559. Staneke, P. O.; Groothuis, G.; Ingemann, S.; Nibbering, N. M. M. J. Phys. Org. Chem. 1996, 9, 471. De Puy, C. H.; Gronert, S.; Mullin, A.; Bierbaum, V. M. J. Am. Chem. Soc. 1990, 112, 8650. Barlow, S. E.; Van Doren, J. M.; Bierbaum, V. M. J. Am. Chem. Soc. 1988, 110, 7240. As pointed out by Brauman and co-workers, the calculations of the gas phase reaction barriers from the experimental data take into account the multiple transition states.
46. For example: Wladkowski, B. D.; Brauman, J. I. J. Phys. Chem. 1993, 97, 13158. Pellerite, M. J.; Brauman, J. I. J. Am. Chem. Soc. 1983, 105, 2672; J. Am. Chem. Soc. 1980, 102, 5993. Dodd, J. A.; Brauman, J. I. J. Am. Chem. Soc. 1984, 106, 5356. Dodd, J. A.; Brauman, J. I. J. Phys. Chem. 1986, 90, 3559. Staneke, P. O.; Groothuis, G.; Ingemann, S.; Nibbering, N. M. M. J. Phys. Org. Chem. 1996, 9, 471. De Puy, C. H.; Gronert, S.; Mullin, A.; Bierbaum, V. M. J. Am. Chem. Soc. 1990, 112, 8650. Barlow, S. E.; Van Doren, J. M.; Bierbaum, V. M. J. Am. Chem. Soc. 1988, 110, 7240. As pointed out by Brauman and co-workers, the calculations of the gas phase reaction barriers from the experimental data take into account the multiple transition states.
47. For example: Wladkowski, B. D.; Brauman, J. I. J. Phys. Chem. 1993, 97, 13158. Pellerite, M. J.; Brauman, J. I. J. Am. Chem. Soc. 1983, 105, 2672; J. Am. Chem. Soc. 1980, 102, 5993. Dodd, J. A.; Brauman, J. I. J. Am. Chem. Soc. 1984, 106, 5356. Dodd, J. A.; Brauman, J. I. J. Phys. Chem. 1986, 90, 3559. Staneke, P. O.; Groothuis, G.; Ingemann, S.; Nibbering, N. M. M. J. Phys. Org. Chem. 1996, 9, 471. De Puy, C. H.; Gronert, S.; Mullin, A.; Bierbaum, V. M. J. Am. Chem. Soc. 1990, 112, 8650. Barlow, S. E.; Van Doren, J. M.; Bierbaum, V. M. J. Am. Chem. Soc. 1988, 110, 7240. As pointed out by Brauman and co-workers, the calculations of the gas phase reaction barriers from the experimental data take into account the multiple transition states.
48. For example: Wladkowski, B. D.; Brauman, J. I. J. Phys. Chem. 1993, 97, 13158. Pellerite, M. J.; Brauman, J. I. J. Am. Chem. Soc. 1983, 105, 2672; J. Am. Chem. Soc. 1980, 102, 5993. Dodd, J. A.; Brauman, J. I. J. Am. Chem. Soc. 1984, 106, 5356. Dodd, J. A.; Brauman, J. I. J. Phys. Chem. 1986, 90, 3559. Staneke, P. O.; Groothuis, G.; Ingemann, S.; Nibbering, N. M. M. J. Phys. Org. Chem. 1996, 9, 471. De Puy, C. H.; Gronert, S.; Mullin, A.; Bierbaum, V. M. J. Am. Chem. Soc. 1990, 112, 8650. Barlow, S. E.; Van Doren, J. M.; Bierbaum, V. M. J. Am. Chem. Soc. 1988, 110, 7240. As pointed out by Brauman and co-workers, the calculations of the gas phase reaction barriers from the experimental data take into account the multiple transition states.
49. For example: Wladkowski, B. D.; Brauman, J. I. J. Phys. Chem. 1993, 97, 13158. Pellerite, M. J.; Brauman, J. I. J. Am. Chem. Soc. 1983, 105, 2672; J. Am. Chem. Soc. 1980, 102, 5993. Dodd, J. A.; Brauman, J. I. J. Am. Chem. Soc. 1984, 106, 5356. Dodd, J. A.; Brauman, J. I. J. Phys. Chem. 1986, 90, 3559. Staneke, P. O.; Groothuis, G.; Ingemann, S.; Nibbering, N. M. M. J. Phys. Org. Chem. 1996, 9, 471. De Puy, C. H.; Gronert, S.; Mullin, A.; Bierbaum, V. M. J. Am. Chem. Soc. 1990, 112, 8650. Barlow, S. E.; Van Doren, J. M.; Bierbaum, V. M. J. Am. Chem. Soc. 1988, 110, 7240. As pointed out by Brauman and co-workers, the calculations of the gas phase reaction barriers from the experimental data take into account the multiple transition states.
50. N2 mechanisms are regarded (for example, in the last reference) as competing on the same potential energy surface along different reaction coordinates (Figure 8 there). The two-state model is also summarized in ref 4a.
51. N2 mechanisms are regarded (for example, in the last reference) as competing on the same potential energy surface along different reaction coordinates (Figure 8 there). The two-state model is also summarized in ref 4a.
52. N2 mechanisms are regarded (for example, in the last reference) as competing on the same potential energy surface along different reaction coordinates (Figure 8 there). The two-state model is also summarized in ref 4a.
53. N2 mechanisms are regarded (for example, in the last reference) as competing on the same potential energy surface along different reaction coordinates (Figure 8 there). The two-state model is also summarized in ref 4a.
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63. 2.
64. 1/2.
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82. 8.6 average are given on p 156.
83. Savéant, J.-M. Private communication.
84. Chidsey, C. E. D. Science 1991, 251, 919; Ibid. 1991, 252, 631. Curvature of ln k vs E° plots for a reaction at an electrode was first established in Savéant, J.-M.; Tesser, D. Discuss. Faraday Soc. 1982, 74, 57. Examples of curved ln k vs E° plots at electrodes (using self-assembled monlayers) are: Richardson, J. N.; Peck, S. R.; Curtin, L. S.; Tender, L. M.; Terrill, R. H.; Carter, M. T.; Murray, R. W.; Rowe, G. K.; Creager, S. E. J. Phys. Chem. 1995, 99, 766. Forster, R. J.; Faulkner, L. R. J. Am. Chem. Soc. 1994, 116, 5444; J. Am. Chem. Soc. 1994, 116, 9411. Smalley, J. F.; Feldberg, S. W.; Chidsey, C. E. D.; Linford, M. R.; Newton, M. D.; Liu, Y. P. J. Phys. Chem. 1995, 99, 13141. Ravenscroft, M. S.; Finklea, H. O. J. Phys. Chem. 1994, 98, 3843. Feng, Z. Q.; Imabayashi, S.; Kakiuchi, T.; Niki, K. J. Elec. Chem. 1995, 394, 149.
85. Chidsey, C. E. D. Science 1991, 251, 919; Ibid. 1991, 252, 631. Curvature of ln k vs E° plots for a reaction at an electrode was first established in Savéant, J.-M.; Tesser, D. Discuss. Faraday Soc. 1982, 74, 57. Examples of curved ln k vs E° plots at electrodes (using self-assembled monlayers) are: Richardson, J. N.; Peck, S. R.; Curtin, L. S.; Tender, L. M.; Terrill, R. H.; Carter, M. T.; Murray, R. W.; Rowe, G. K.; Creager, S. E. J. Phys. Chem. 1995, 99, 766. Forster, R. J.; Faulkner, L. R. J. Am. Chem. Soc. 1994, 116, 5444; J. Am. Chem. Soc. 1994, 116, 9411. Smalley, J. F.; Feldberg, S. W.; Chidsey, C. E. D.; Linford, M. R.; Newton, M. D.; Liu, Y. P. J. Phys. Chem. 1995, 99, 13141. Ravenscroft, M. S.; Finklea, H. O. J. Phys. Chem. 1994, 98, 3843. Feng, Z. Q.; Imabayashi, S.; Kakiuchi, T.; Niki, K. J. Elec. Chem. 1995, 394, 149.
86. Chidsey, C. E. D. Science 1991, 251, 919; Ibid. 1991, 252, 631. Curvature of ln k vs E° plots for a reaction at an electrode was first established in Savéant, J.-M.; Tesser, D. Discuss. Faraday Soc. 1982, 74, 57. Examples of curved ln k vs E° plots at electrodes (using self-assembled monlayers) are: Richardson, J. N.; Peck, S. R.; Curtin, L. S.; Tender, L. M.; Terrill, R. H.; Carter, M. T.; Murray, R. W.; Rowe, G. K.; Creager, S. E. J. Phys. Chem. 1995, 99, 766. Forster, R. J.; Faulkner, L. R. J. Am. Chem. Soc. 1994, 116, 5444; J. Am. Chem. Soc. 1994, 116, 9411. Smalley, J. F.; Feldberg, S. W.; Chidsey, C. E. D.; Linford, M. R.; Newton, M. D.; Liu, Y. P. J. Phys. Chem. 1995, 99, 13141. Ravenscroft, M. S.; Finklea, H. O. J. Phys. Chem. 1994, 98, 3843. Feng, Z. Q.; Imabayashi, S.; Kakiuchi, T.; Niki, K. J. Elec. Chem. 1995, 394, 149.
87. Chidsey, C. E. D. Science 1991, 251, 919; Ibid. 1991, 252, 631. Curvature of ln k vs E° plots for a reaction at an electrode was first established in Savéant, J.-M.; Tesser, D. Discuss. Faraday Soc. 1982, 74, 57. Examples of curved ln k vs E° plots at electrodes (using self-assembled monlayers) are: Richardson, J. N.; Peck, S. R.; Curtin, L. S.; Tender, L. M.; Terrill, R. H.; Carter, M. T.; Murray, R. W.; Rowe, G. K.; Creager, S. E. J. Phys. Chem. 1995, 99, 766. Forster, R. J.; Faulkner, L. R. J. Am. Chem. Soc. 1994, 116, 5444; J. Am. Chem. Soc. 1994, 116, 9411. Smalley, J. F.; Feldberg, S. W.; Chidsey, C. E. D.; Linford, M. R.; Newton, M. D.; Liu, Y. P. J. Phys. Chem. 1995, 99, 13141. Ravenscroft, M. S.; Finklea, H. O. J. Phys. Chem. 1994, 98, 3843. Feng, Z. Q.; Imabayashi, S.; Kakiuchi, T.; Niki, K. J. Elec. Chem. 1995, 394, 149.
88. Chidsey, C. E. D. Science 1991, 251, 919; Ibid. 1991, 252, 631. Curvature of ln k vs E° plots for a reaction at an electrode was first established in Savéant, J.-M.; Tesser, D. Discuss. Faraday Soc. 1982, 74, 57. Examples of curved ln k vs E° plots at electrodes (using self-assembled monlayers) are: Richardson, J. N.; Peck, S. R.; Curtin, L. S.; Tender, L. M.; Terrill, R. H.; Carter, M. T.; Murray, R. W.; Rowe, G. K.; Creager, S. E. J. Phys. Chem. 1995, 99, 766. Forster, R. J.; Faulkner, L. R. J. Am. Chem. Soc. 1994, 116, 5444; J. Am. Chem. Soc. 1994, 116, 9411. Smalley, J. F.; Feldberg, S. W.; Chidsey, C. E. D.; Linford, M. R.; Newton, M. D.; Liu, Y. P. J. Phys. Chem. 1995, 99, 13141. Ravenscroft, M. S.; Finklea, H. O. J. Phys. Chem. 1994, 98, 3843. Feng, Z. Q.; Imabayashi, S.; Kakiuchi, T.; Niki, K. J. Elec. Chem. 1995, 394, 149.
89. Chidsey, C. E. D. Science 1991, 251, 919; Ibid. 1991, 252, 631. Curvature of ln k vs E° plots for a reaction at an electrode was first established in Savéant, J.-M.; Tesser, D. Discuss. Faraday Soc. 1982, 74, 57. Examples of curved ln k vs E° plots at electrodes (using self-assembled monlayers) are: Richardson, J. N.; Peck, S. R.; Curtin, L. S.; Tender, L. M.; Terrill, R. H.; Carter, M. T.; Murray, R. W.; Rowe, G. K.; Creager, S. E. J. Phys. Chem. 1995, 99, 766. Forster, R. J.; Faulkner, L. R. J. Am. Chem. Soc. 1994, 116, 5444; J. Am. Chem. Soc. 1994, 116, 9411. Smalley, J. F.; Feldberg, S. W.; Chidsey, C. E. D.; Linford, M. R.; Newton, M. D.; Liu, Y. P. J. Phys. Chem. 1995, 99, 13141. Ravenscroft, M. S.; Finklea, H. O. J. Phys. Chem. 1994, 98, 3843. Feng, Z. Q.; Imabayashi, S.; Kakiuchi, T.; Niki, K. J. Elec. Chem. 1995, 394, 149.
90. Chidsey, C. E. D. Science 1991, 251, 919; Ibid. 1991, 252, 631. Curvature of ln k vs E° plots for a reaction at an electrode was first established in Savéant, J.-M.; Tesser, D. Discuss. Faraday Soc. 1982, 74, 57. Examples of curved ln k vs E° plots at electrodes (using self-assembled monlayers) are: Richardson, J. N.; Peck, S. R.; Curtin, L. S.; Tender, L. M.; Terrill, R. H.; Carter, M. T.; Murray, R. W.; Rowe, G. K.; Creager, S. E. J. Phys. Chem. 1995, 99, 766. Forster, R. J.; Faulkner, L. R. J. Am. Chem. Soc. 1994, 116, 5444; J. Am. Chem. Soc. 1994, 116, 9411. Smalley, J. F.; Feldberg, S. W.; Chidsey, C. E. D.; Linford, M. R.; Newton, M. D.; Liu, Y. P. J. Phys. Chem. 1995, 99, 13141. Ravenscroft, M. S.; Finklea, H. O. J. Phys. Chem. 1994, 98, 3843. Feng, Z. Q.; Imabayashi, S.; Kakiuchi, T.; Niki, K. J. Elec. Chem. 1995, 394, 149.
91. Chidsey, C. E. D. Science 1991, 251, 919; Ibid. 1991, 252, 631. Curvature of ln k vs E° plots for a reaction at an electrode was first established in Savéant, J.-M.; Tesser, D. Discuss. Faraday Soc. 1982, 74, 57. Examples of curved ln k vs E° plots at electrodes (using self-assembled monlayers) are: Richardson, J. N.; Peck, S. R.; Curtin, L. S.; Tender, L. M.; Terrill, R. H.; Carter, M. T.; Murray, R. W.; Rowe, G. K.; Creager, S. E. J. Phys. Chem. 1995, 99, 766. Forster, R. J.; Faulkner, L. R. J. Am. Chem. Soc. 1994, 116, 5444; J. Am. Chem. Soc. 1994, 116, 9411. Smalley, J. F.; Feldberg, S. W.; Chidsey, C. E. D.; Linford, M. R.; Newton, M. D.; Liu, Y. P. J. Phys. Chem. 1995, 99, 13141. Ravenscroft, M. S.; Finklea, H. O. J. Phys. Chem. 1994, 98, 3843. Feng, Z. Q.; Imabayashi, S.; Kakiuchi, T.; Niki, K. J. Elec. Chem. 1995, 394, 149.
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