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Volumn 62, Issue 7, 1997, Pages 2210-2221

Direct Observation of Ultrafast Decarboxylation of Acyloxy Radicals via Photoinduced Electron Transfer in Carboxylate Ion Pairs

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EID: 0000834065     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9617833     Document Type: Article
Times cited : (83)

References (133)
  • 35
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    • note
    • 4g,15 has established that CT excitation of the EDA complex effects the transfer of an electron from the donor to the acceptor in less than 500 fs.
  • 36
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    • ox) in solution. See: (a) Mulliken, R. S. J. Am. Chem. Soc. 1952, 74, 811. (b) Mulliken, R. S.; Person, W. B. Molecular Complexes: A Lecture and Reprint Volume; Wiley: New York, 1969.
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    • note
    • CC) on the picosecond time scale cannot be readily extracted. For a discussion of this problem in the context of peroxide decomposition, see ref 9.
  • 57
    • 1542677162 scopus 로고    scopus 로고
    • note
    • 24b methylviologen triflate showed no interfering CT bands between anion and cation.
  • 62
    • 1542677163 scopus 로고    scopus 로고
    • note
    • -1. See ref 24b.]
  • 64
    • 1542467628 scopus 로고    scopus 로고
    • note
    • 29b was unnecessary,
  • 66
    • 1542782462 scopus 로고    scopus 로고
    • note
    • exc > 370 nm). The experiment thus was carried out with the frequency-tripled output of a 25-ps mode-locked Nd:YAG laser.
  • 67
    • 1542677164 scopus 로고    scopus 로고
    • note
    • max = 650 nm, due to intermolecular association, would be too weak to be observed with our apparatus.
  • 71
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    • note
    • 28
  • 72
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    • See also: (b) Davidson, R. S.; Santhanam, M. J. Chem. Soc., Perkin Trans. 2 1972, 2355 for its spectrum in various nonaqueous solvents. (c) For the spectrum of the triethylsilyl-substituted analogue, see: Chatgilialoglu, C.; Ingold, K. U.; Scaiano, J. C. J. Am. Chem. Soc. 1982, 104, 5119.
    • (1972) J. Chem. Soc., Perkin Trans. , vol.2 , pp. 2355
    • Davidson, R.S.1    Santhanam, M.2
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    • See also: (b) Davidson, R. S.; Santhanam, M. J. Chem. Soc., Perkin Trans. 2 1972, 2355 for its spectrum in various nonaqueous solvents. (c) For the spectrum of the triethylsilyl-substituted analogue, see: Chatgilialoglu, C.; Ingold, K. U.; Scaiano, J. C. J. Am. Chem. Soc. 1982, 104, 5119.
    • (1982) J. Am. Chem. Soc. , vol.104 , pp. 5119
    • Chatgilialoglu, C.1    Ingold, K.U.2    Scaiano, J.C.3
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    • In accord with the Mulliken formulation of the charge-transfer transition in ref 13
    • In accord with the Mulliken formulation of the charge-transfer transition in ref 13.
  • 79
    • 1542467630 scopus 로고    scopus 로고
    • note
    • 2+ and tetramethoxybenzilate was an exception, and the orange solution remained unchanged in color even after prolonged irradiation.
  • 82
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    • Scaiano, J. C., ed; CRC Press: Boca Raton, FL
    • Eaton, D. R., in CRC Handbook of Photochemistry, Vol 1; Scaiano, J. C., ed; CRC Press: Boca Raton, FL, 1989, p. 1233.
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  • 83
    • 1542677165 scopus 로고    scopus 로고
    • note
    • .+ absorbed more than 90% of the incident actinic light and the reaction effectively ceased.]
  • 89
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    • note
    • (b) Ketyl radicals are electron rich by virtue of their very low oxidation potentials and ease of oxidation in solution.
  • 91
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    • See: (c) Baumann, H.; Merckel, C.; Timpe, H.-J.; Graness, A.; Kleinschmidt, J.; Gould, I. R.; Turro, N. J. Chem. Phys. Lett. 1984, 103, 497. (d) Kemp, T. J.; Martins, L. J. A. J. Chem. Soc., Perkin Trans. 2 1980, 1708. (e) Engel, P. S.; Wu, W. X. J. Am. Chem. Soc. 1989, 111, 1830.
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    • See: (c) Baumann, H.; Merckel, C.; Timpe, H.-J.; Graness, A.; Kleinschmidt, J.; Gould, I. R.; Turro, N. J. Chem. Phys. Lett. 1984, 103, 497. (d) Kemp, T. J.; Martins, L. J. A. J. Chem. Soc., Perkin Trans. 2 1980, 1708. (e) Engel, P. S.; Wu, W. X. J. Am. Chem. Soc. 1989, 111, 1830.
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    • Engel, P.S.1    Wu, W.X.2
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    • The escape of the benziloxy 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.
    • (1989) J. Phys. Chem. , vol.93 , pp. 1393
    • Scott, T.W.1    Liu, S.N.2
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    • note
    • .+, arylacetoxy] radical pairs.
  • 98
    • 1542572174 scopus 로고    scopus 로고
    • Calculated by means of the Eyring equation in ref 49
    • Calculated by means of the Eyring equation in ref 49.
  • 102
    • 1542467633 scopus 로고    scopus 로고
    • note
    • -1) results in a similar (though less pronounced) effect (see Table 5).
  • 103
    • 1542677166 scopus 로고    scopus 로고
    • note
    • 56
  • 104
    • 1542467634 scopus 로고    scopus 로고
    • note
    • CT < 360 nm and thus could not be excited with the Ti:sapphire laser.
  • 107
    • 1542782465 scopus 로고    scopus 로고
    • note
    • 11c Alternatively, the rate of the clock reaction used by these authors (decarboxylation of the 9-methylfluorenecarboxyl radical) may be somewhat overestimated. (See footnote 20 in ref 9.)
  • 108
    • 1542467638 scopus 로고    scopus 로고
    • note
    • + = -1.73 for the back-electron transfer.
  • 124
    • 1542467637 scopus 로고    scopus 로고
    • note
    • (a) It is remarkable that the competing processes of back-electron transfer and carbon-carbon bond cleavage are completely independent and the rate of one process is not affected by the presence of the other.
  • 125
    • 1542572175 scopus 로고    scopus 로고
    • note
    • 64
  • 131
    • 1542782467 scopus 로고    scopus 로고
    • Elemental analyses were performed by Atlantic Microlabs, Norcross, GA
    • Elemental analyses were performed by Atlantic Microlabs, Norcross, GA.


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