Bimolecular electron transfers that deviate from the sandros-boltzmann dependence on free energy: Steric effect

Journal of Organic Chemistry

Volumn 77, Issue 4, 2012, Pages 1632-1639

  Luo, Pu ^a   Dinnocenzo, Joseph P ^a   Merkel, Paul B ^a   Young, Ralph H ^a   Farid, Samir ^a  

^a UNIVERSITY OF ROCHESTER   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

1 ,4-DI-TERT-BUTYLBENZENE; CONTACT PAIR; ELECTRON TRANSFER; INTERPLANAR SEPARATION; MATRIX ELEMENTS; ORBITAL OVERLAP; PROPYLENE CARBONATE; RADICAL CATIONS; REACTION FREE ENERGY; REORGANIZATION ENERGIES; SOLVENT VISCOSITY; STERIC EFFECT; STERIC HINDRANCES;

ACETONITRILE; BENZENE; FREE ENERGY; FREE RADICAL REACTIONS; ORGANIC SOLVENTS; RATE CONSTANTS; SEPARATION;

ELECTRON TRANSITIONS;

ACETONITRILE; BENZENE DERIVATIVE; BIPHENYL DERIVATIVE; PROPYLENE CARBONATE;

ARTICLE; CALCULATION; CHEMICAL ANALYSIS; CHEMICAL REACTION; ELECTRON TRANSPORT; ENERGY;

EID: 84857212956     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo202385f     Document Type: Article

References (53)

1. Farid, S.; Dinnocenzo, J. P.; Merkel, P. M.; Young, R. H.; Shukla, D. J. Am. Chem. Soc. 2011, 133, 4791
2. Farid, S.; Dinnocenzo, J. P.; Merkel, P. M.; Young, R. H.; Shukla, D.; Guirado, G. J. Am. Chem. Soc. 2011, 133, 11580
3. Equation 2 is similar to an expression first proposed by Sandros(3b) for triplet energy transfer without an apparent activation barrier.
4. Sandros, K. Acta Chem. Scand. 1964, 18, 2355
5. Merkel, P. B.; Luo, P.; Dinnocenzo, J. P.; Farid, S. J. Org. Chem. 2009, 74, 5163
6. Guirado, G.; Fleming, C. N.; Lingenfelter, T. G.; Williams, M. L.; Zuilhof, H.; Dinnocenzo, J. P. J. Am. Chem. Soc. 2004, 126, 14086
7. Amatore, C.; Lefrou, C. J. Electroanal. Chem. 1992, 325, 239
8. Barnes, J. C.; Chudek, J. A.; Hunter, G.; Blake, A. J.; Dyson, P. J.; Johnson, B. F. G.; Weissensteiner, W. J. Chem. Soc. Faraday Trans. 1995, 91, 2149
9. Gould, I. R.; Young, R. H.; Moody, R. E.; Farid, S. J. Phys. Chem. 1991, 95, 2068
10. At 20 °C, the viscosity (dynamic) of propylene carbonate is 2.764 cP(11b) and that of acetonitrile is 0.353 cP.(11c)
11. Moumouzias, G.; Ritzoulis, G. J. Chem. Eng. Data 1992, 37, 482
12. Rudakov, O. B.; Sokolov, M. I.; Selemenev, V. F. Russ. J. Phys. Chem. 1999, 73, 1473
13. Based on MO calculations(12b) (B3LYP/6-31G) using van der Waals radii of 1.77 Å for carbon and 1.01 Å for hydrogen.(12c)
14. Spartan'10; Wavefunction, Inc.: Irvine, CA.(12d)
15. Bondi, A. J. Phys. Chem. 1964, 68, 441
16. Shao, Y.; Molnar, L. F.; Jung, Y.; Kussmann, J.; Ochsenfeld, C.; Brown, S. T.; Gilbert, A. T. B.; Slipchenko, L. V.; Levchenko, S. V.; O'Neill, D. P.; DiStasio, R. A., Jr.; Lochan, R. C.; Wang, T.; Beran, G. J. O.; Besley, N. A.; Herbert, J. M.; Lin, C. Y.; Van Voorhis, T.; Chien, S. H.; Sodt, A.; Steele, R. P.; Rassolov, V. A.; Maslen, P. E.; Korambath, P. P.; Adamson, R. D.; Austin, B.; Baker, J.; Byrd, E. F. C.; Dachsel, H.; Doerksen, R. J.; Dreuw, A.; Dunietz, B. D.; Dutoi, A. D.; Furlani, T. R.; Gwaltney, S. R.; Heyden, A.; Hirata, S.; Hsu, C.-P.; Kedziora, G.; Khalliulin, R. Z.; Klunzinger, P.; Lee, A. M.; Lee, M. S.; Liang, W. Z.; Lotan, I.; Nair, N.; Peters, B.; Proynov, E. I.; Pieniazek, P. A.; Rhee, Y. M.; Ritchie, J.; Rosta, E.; Sherrill, C. D.; Simmonett, A. C.; Subotnik, J. E.; Woodcock, H. L., III; Zhang, W.; Bell, A. T.; Chakraborty, A. K.; Chipman, D. M.; Keil, F. J.; Warshel, A.; Hehre, W. J.; Schaefer, H. F.; Kong, J.; Krylov, A. I.; Gill, P. M. W.; Head-Gordon, M. Phys. Chem. Chem. Phys. 2006, 8, 3172
17. In agreement with our modeling, the extended separation distance for a complex of C2 with a planar aromatic acceptor relative to that of a nonhindered benzene derivative has been previously estimated to be ∼1 Å.(12f)
18. Rathore, R.; Lindeman, S. V.; Kochi, J. K. J. Am. Chem. Soc. 1997, 119, 9393
19. Hopfield, J. J. Proc. Natl. Acad. Sci. U.S.A. 1974, 71, 3640
20. Van Duyne, R. P.; Fischer, S. F. Chem. Phys. 1974, 5, 183
21. Ulstrup, J.; Jortner, J. J. Chem. Phys. 1975, 63, 4358
22. Siders, P.; Marcus, R. A. J. Am. Chem. Soc. 1981, 103 (741) 748
23. Marcus, R. A. J. Chem. Phys. 1984, 81, 4494
24. Marcus, R. A.; Sutin, N. Biochim. Biophys. Acta 1985, 811, 265
25. The twist angle in biphenyl is ∼40°(14b, 14c) and in its radical cation is ∼19°.(14d, 14e)
26. Bastiansen, O. Acta Chem. Scand. 1949, 3, 408
27. Arulmozhiraja, S.; Fujii, T.; Morita, M. J. Phys. Chem. A 2002, 106, 10590
28. Furuya, K.; Torii, H.; Furukawa, Y.; Tasumi, M. THEOCHEM 1998, 424, 225
29. Arulmozhiraja, S.; Fujii, T.; Morita, M. J. Phys. Chem. A 2002, 106, 10590
30. Gould, I. R.; Farid, S. J. Am. Chem. Soc. 1988, 110, 1991
31. Gould, I. R.; Ege, D.; Moser, J. E.; Farid, S. J. Am. Chem. Soc. 1990, 112, 4290
32. Gould, I. R.; Farid, S. Acc. Chem. Res. 1996, 29, 522
33. Marcus, R. A. J. Chem. Phys. 1956, 24, 966
34. D) of propylene carbonate and acetonitrile are 1.421 and 1.344, respectively.(17b) Their respective dielectric constants (ε) at 20 °C are 62.9 and 36.0.(17b)
35. Laurence, C.; Nicolet, P.; Dalati, M. T.; Abboud, J.-L. M.; Notario, R. J. Phys. Chem. 1994, 98, 5807
36. Newton, M.; Sutin, N. Annu. Rev. Phys. Chem. 1984, 35, 437
37. Miller, J. R.; Beitz, J. V.; Huddleston, R. K. J. Am. Chem. Soc. 1984, 106, 5057
38. Moser, C. C.; Keske, J. M.; Warncke, K.; Farid, R. S. Nature 1992, 355, 796
39. McManis, G. E.; Nielson, R. M.; Gochev, A.; Weaver, M. J. J. Am. Chem. Soc. 1989, 111, 5533
40. et in propylene carbonate vs acetonitrile is reminiscent of the 4.2-fold slower initial relaxation of the solvent around an excited coumarin-153 molecule.(22b)
41. Gardecki, J. A.; Maroncelli, M. Chem. Phys. Lett. 1999, 301, 571
42. •+), an analogous decrease in the rate constants for return electron transfer was observed between sterically hindered and nonhindered reactants.(23b, 23c)
43. Gould, I. R.; Farid, S. J. Phys. Chem. 1993, 97, 13067
44. Gould, I. R.; Moser, J. E.; Armitage, B.; Farid, S. Res. Chem. Intermed. 1995, 21, 793
45. Jacques, P.; Allonas, X.; Suppan, P.; Von Raumer, M. J. Photochem. Photobiol., A 1996, 101, 183
46. Hubig, S. M.; Rathore, R.; Kochi, J. K. J. Am. Chem. Soc. 1999, 121, 617
47. Zhou, J.; Shah, R. P.; Findley, B. R.; Braun, C. L. J. Phys. Chem. A 2002, 106, 12
48. Nelsen, S. F. Acc. Chem. Res. 1981, 14, 131
49. Grampp, G.; Grossmann, B.; Heinze, J.; Landgraf, S.; Rasmussen, K. ChemPhysChem. 2008, 9, 854
50. Pangborn, A. B.; Giardello, M. A.; Grubbs, R. H.; Rosen, R. K.; Timmers, F. J. Organometallics 1996, 15, 1518
51. Alaimo, P. J.; Peters, D. W.; Arnold, J.; Bergman, R. G. J. Chem. Educ. 2001, 78, 64
52. Levy, L. A. J. Org. Chem. 1978, 43, 3068
53. Kim, H. S.; Kim, Y. H.; Ahn, S. K.; Kwon, S. K. Macromolecules 2003, 36, 2327