Direct observation of carbon - Carbon bond cleavage in ultrafast decarboxylations

Journal of the American Chemical Society

Volumn 118, Issue 18, 1996, Pages 4502-4503

  Michael Bookman, T ^a   Hubig, Stephan M ^a   Kochi, Jay K ^a  

^a University of Houston   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ARTICLE; CHEMICAL BOND; CHEMICAL STRUCTURE; DECARBOXYLATION; ELECTRON TRANSPORT; NONHUMAN; SPECTRAL SENSITIVITY; SPECTROSCOPY;

EID: 15844415139     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja960112j     Document Type: Article

References (66)

1. (a) Manz, J.; Wöste, L. Femtosecond Chemistry; VCH: Weinheim, 1995.
2. (b) Simon, J. D. Rev. Sci. Instrum. 1989, 60, 3597.
3. (a) Kliner, D. A. V.; Alfano, J. C.; Barbara, P. F. J. Chem. Phys. 1993, 98, 5375.
4. (b) Sension, R. J.; Repinec, S. T.; Szarka, A. Z.; Hochstrasser, R. M. J. Chem. Phys. 1993, 98, 6291.
5. (c) Joly, A. G.; Nelson, K. A. Chem. Phys. 1991, 152, 69.
6. (d) Schwartz, B. J.; Peteanu, L. A.; Harris, C. B. J. Phys. Chem. 1992, 96, 3591.
7. (e) Schoenlein, R. W.; Peteanu, L. A.; Wang, Q.; Mathies, R. A.; Shank, C. V. J. Phys. Chem. 1993, 97, 12087.
8. (f) Laermer, F.; Elsaesser, T.; Kaiser, W. Chem. Phys. Lett. 1988, 148, 119.
9. (g) Lenderink, E.; Duppen, K.; Wiersma, D. A. Chem. Phys. Lett. 1993, 211, 503.
10. (h) Sakata, Y.; Tsue, H.; Oneil, M. P.; Wiederrecht, G. P.; Wasielewski, M. R. J. Am. Chem. Soc. 1994, 116, 6904.
11. (a) Braun, W.; Rajbenbaeh, L.; Eirich, F. R. J. Phys. Chem. 1962, 66, 1591.
12. (b) Kaptein, R.; Brokken-Zijp, J.; de Kanter, F. J. J. J. Am. Chem. Soc 1972, 94, 6280.
13. (c) Falvey, D. E.; Schuster, G. B. J. Am. Chem. Soc. 1986, 108, 7419.
14. (d) Hilbom, J. W.; Pincock, J. A. J. Am. Chem. Soc. 1991, 113, 2683.
15. (e) Budac, D.; Wan, P. J. Photochem. Photobiol. A 1992, 67, 135.
16. See: (a) Barnett, J. R.; Hopkins, A. S.; Ledwith, A. J. Chem. Soc. Perkin Trans. 2 1973, 80. (b) Deronzier, A.; Esposito, F. Nouv. J. Chem. 1983, 7, 15. (c) Jones, G., II; Zisk, M. B. J. Org. Chem. 1986, 51, 947. (d) Mandler, D.; Willner, I. J. Chem. Soc. Perkin Trans. 2 1988, 997.
17. See: (a) Barnett, J. R.; Hopkins, A. S.; Ledwith, A. J. Chem. Soc. Perkin Trans. 2 1973, 80. (b) Deronzier, A.; Esposito, F. Nouv. J. Chem. 1983, 7, 15. (c) Jones, G., II; Zisk, M. B. J. Org. Chem. 1986, 51, 947. (d) Mandler, D.; Willner, I. J. Chem. Soc. Perkin Trans. 2 1988, 997.
18. See: (a) Barnett, J. R.; Hopkins, A. S.; Ledwith, A. J. Chem. Soc. Perkin Trans. 2 1973, 80. (b) Deronzier, A.; Esposito, F. Nouv. J. Chem. 1983, 7, 15. (c) Jones, G., II; Zisk, M. B. J. Org. Chem. 1986, 51, 947. (d) Mandler, D.; Willner, I. J. Chem. Soc. Perkin Trans. 2 1988, 997.
19. See: (a) Barnett, J. R.; Hopkins, A. S.; Ledwith, A. J. Chem. Soc. Perkin Trans. 2 1973, 80. (b) Deronzier, A.; Esposito, F. Nouv. J. Chem. 1983, 7, 15. (c) Jones, G., II; Zisk, M. B. J. Org. Chem. 1986, 51, 947. (d) Mandler, D.; Willner, I. J. Chem. Soc. Perkin Trans. 2 1988, 997.
20. CC) on the picosecond time scale cannot be readily extracted. For a discussion of this problem in the context of peroxide decomposition, see ref 3c.
21. Pacansky, J.; Brown, D. W. J. Phys. Chem. 1983, 87, 1553. See also: Sheldon, R. A.; Kochi, J. K. J. Am. Chem. Soc. 1970, 92, 5175.
22. Pacansky, J.; Brown, D. W. J. Phys. Chem. 1983, 87, 1553. See also: Sheldon, R. A.; Kochi, J. K. J. Am. Chem. Soc. 1970, 92, 5175.
23. 9
24. (a) Ojima, S.; Miyasaka, H.; Mataga, N. J. Phys. Chem. 1990, 94, 4147.
25. (b) Wynne, K.; Galli, C.; Hochstrasser, R. M. J. Chem. Phys. 1994, 100, 4797.
26. See also: (c) Hilinski, E. F.; Masnovi, J. M.; Amatore, C.; Kochi, J. K.; Rentzepis, P. M. J. Am. Chem. Soc. 1983, 105, 6167. (d) Hilinski, E. F.; Masnovi, J. M.; Kochi, J. K.; Rentzepis, P. M. J. Am. Chem. Soc. 1984, 106, 8071.
27. See also: (c) Hilinski, E. F.; Masnovi, J. M.; Amatore, C.; Kochi, J. K.; Rentzepis, P. M. J. Am. Chem. Soc. 1983, 105, 6167. (d) Hilinski, E. F.; Masnovi, J. M.; Kochi, J. K.; Rentzepis, P. M. J. Am. Chem. Soc. 1984, 106, 8071.
28. (a) Mulliken, R. S. J. Am. Chem. Soc. 1952, 74, 811.
29. (b) Mulliken, R. S.; Person, W. B. Molecular Complexes: A Lecture and Reprint Volume; Wiley: New York, 1969
30. (c) Mulliken, R. S. J. Am. Chem. Soc. 1950, 72, 600.
31. The laser spectrometer consists of a Ti:sapphire oscillator and two amplifiers. The oscillator is pumped by an argon ion laser to generate 110-fs pulses tunable between 720 and 920 nm. These pulses are amplified sequentially by a regenerative amplifier and a linear (multipass) amplifier, both of which are pumped by the frequency-doubled output of a (10 Hz) Q-switched Nd:YAG laser. The laser system produces 230-fs pulses with energies up to 10 mJ which are frequency-doubled (360-460 nm) for excitation.
32. Moore, J. W.; Pearson, R. G. Kinetics and Mechanism, 3rd ed.; Wiley: New York, 1981; p 173.
33. (a) Ebbesen, T. W.; Ferraudi, G. J. Phys. Chem. 1983, 87, 3717.
34. (b) Ebbesen, T. W.; Manring, L. E.; Peters, K. S. J. Am. Chem. Soc. 1984, 106, 7400.
35. (c) Hubig, S. M. J. Phys. Chem. 1992, 96, 2903.
36. (d) Hubig, S. M.; Kochi, J. K. J. Phys. Chem. 1995, 99, 17578.
37. (a) Michaelis, L. Biochem. Z. 1932, 250, 564.
38. (b) Michaelis, L.; Hill, E. S. J. Gen. Physiol. 1933, 16, 859.
39. (c) Bookman, T. M.; Kochi, J. K. J. Org. Chem. 1990, 55, 4127.
40. (d) Watanabe, T.; Honda, K. J. Phys. Chem. 1982, 86, 2617.
41. (a) Johnston, L. J.; Lougnot, D. L.; Wintgens, V.; Scaiano, J. C. J. Am. Chem. Soc. 1988, 110, 518.
42. (b) Nagarajan, V.; Fessenden, R. W. Chem. Phys. Lett. 1984, 112, 207.
43. -1. Since the experimental spectrum in Figure 1 is unchanged over a period of more than 50 ps, correction for group velocity dispersion is unnecessary.
44. (b) Hayon, E.; Ibata, T.; Lichtin, N. N., Simic, M. J. Phys. Chem. 1972, 76, 2072.
45. 15b
46. ̇) is strongly blue-shifted away from the absorption band of the ketyl radical. See: Itoh, M.; Naeakura, S. Bull. Chem. Soc. Jpn. 1966, 39, 369.
47. (a) The transient absorbance of reduced methylviologen is simulated simply as the integral over time of the laser profile.
48. 15b
49. (c) The kinetic trace of the ketyl radical in Figure 2 is displaced by 0.4 ps to accommodate the difference in the group velocity dispersion of the 530-nm monitoring wavelength relative to that at 605 nm. [Note that the later rise of the 530-nm absorbance is opposite to mat based on the consideration of group velocity dispersion and thus cannot be due to an instrumental artifact ("chirp"). See: Sharma, D. K.; Yip, R. W.; Williams, D. F.; Sugamori, S. E.; Bradley, L. L. T. Chem. Phys. Lett. 1976, 41, 460. For an example of chirp-induced spectral distortion, see: Miyasaka, H.; Ojima, S.; Mataga, N. J. Phys. Chem. 1989, 93, 3380. Yip, R. W ; Korppi-Tommola, J. Rev. Chem. Intermed. 1985, 6, 33.]
50. (c) The kinetic trace of the ketyl radical in Figure 2 is displaced by 0.4 ps to accommodate the difference in the group velocity dispersion of the 530-nm monitoring wavelength relative to that at 605 nm. [Note that the later rise of the 530-nm absorbance is opposite to mat based on the consideration of group velocity dispersion and thus cannot be due to an instrumental artifact ("chirp"). See: Sharma, D. K.; Yip, R. W.; Williams, D. F.; Sugamori, S. E.; Bradley, L. L. T. Chem. Phys. Lett. 1976, 41, 460. For an example of chirp-induced spectral distortion, see: Miyasaka, H.; Ojima, S.; Mataga, N. J. Phys. Chem. 1989, 93, 3380. Yip, R. W ; Korppi-Tommola, J. Rev. Chem. Intermed. 1985, 6, 33.]
51. (c) The kinetic trace of the ketyl radical in Figure 2 is displaced by 0.4 ps to accommodate the difference in the group velocity dispersion of the 530-nm monitoring wavelength relative to that at 605 nm. [Note that the later rise of the 530-nm absorbance is opposite to mat based on the consideration of group velocity dispersion and thus cannot be due to an instrumental artifact ("chirp"). See: Sharma, D. K.; Yip, R. W.; Williams, D. F.; Sugamori, S. E.; Bradley, L. L. T. Chem. Phys. Lett. 1976, 41, 460. For an example of chirp-induced spectral distortion, see: Miyasaka, H.; Ojima, S.; Mataga, N. J. Phys. Chem. 1989, 93, 3380. Yip, R. W ; Korppi-Tommola, J. Rev. Chem. Intermed. 1985, 6, 33.]
52. ̇ is obtained by nanosecond laser photolysis using benzophenone triplet as actinometer. See; Hurley, J. K.; Sinai, N.; Linshitz, H. Photochem. Photobiol. 1983, 38, 9. The escape of the radicals out of the solvent cage is not included in the femtosecond kinetics, since it occurs on much slower time scales. See: Scott, T. W.; Liu, S. N. J. Phys. Chem. 1989, 93, 1393.
53. ̇ is obtained by nanosecond laser photolysis using benzophenone triplet as actinometer. See; Hurley, J. K.; Sinai, N.; Linshitz, H. Photochem. Photobiol. 1983, 38, 9. The escape of the radicals out of the solvent cage is not included in the femtosecond kinetics, since it occurs on much slower time scales. See: Scott, T. W.; Liu, S. N. J. Phys. Chem. 1989, 93, 1393.
54. CC was directly obtained from the rise of the ketyl radical (see Figure 2), since back electron transfer is negligible as described in ref 17.
55. 3c on the picosecond time scale.
56. CT < 360 nm and thus could not be excited with the Ti:sapphire laser system (see footnote 10).
57. 21a and ease of oxidation in soluuon. See: (a) Baumann, H.; Merckel, C.; Timpe, H -J.; Graness, A., Klemschmidt, J.; Gould, I. R.; Turro, N. J. Chem. Phys. Lett. 1984, 103, 497.
58. (b) Kemp, T. J., Martins, L. J. A. J. Chem. Soc. Perkin Trans. 2 1980, 1708.
59. (c) Engel, P. S.; Wu, W. X. J. Am. Chem. Soc. 1989, 111, 1830.
60. (a) Marcus, R. A. Annu. Rev. Phys. Chem. 1964, 15, 155.
61. (b) Marcus, R. A. J. Chem. Phys. 1965, 43, 679.
62. (c) Marcus, R. A. Faraday Discuss. Chem. Soc. 1982, 74, 7.
63. (d) Marcus, R. A. J. Chem. Phys. 1956, 24, 966.
64. 23b
65. (b) Asahi, T.; Ohkohchi, M.; Mataga, N. J. Phys. Chem. 1993, 97, 13132 and references therein.
66. Polanyi, J. C.; Zewail, A. H. Acc. Chem. Res. 1995, 28, 119.