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Volumn 102, Issue 28, 1998, Pages 5456-5464

Concentration-dependent isotope effects. The photocyanation of naphthalene

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Indexed keywords


EID: 0000402026     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp9800259     Document Type: Article
Times cited : (5)

References (87)
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    • Descriptions of reactions of radical cations with nucleophiles using this method were shown to be in accordance with experimentally observed reaction patterns; for example, see: (b) Zuilhof, H.; Vertegaal, L. B. J.; Van der Gen, A.; Lodder, G. J. Org. Chem. 1993, 58, 2804-2809. (c) Dinnocenzo, J. P.; Zuilhof, H.; Lieberman, D. R.; Simpson, T. R.; McKechney, M. W. J. Am. Chem. Soc. 1997, 119, 994-1004.
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    • Descriptions of reactions of radical cations with nucleophiles using this method were shown to be in accordance with experimentally observed reaction patterns; for example, see: (b) Zuilhof, H.; Vertegaal, L. B. J.; Van der Gen, A.; Lodder, G. J. Org. Chem. 1993, 58, 2804-2809. (c) Dinnocenzo, J. P.; Zuilhof, H.; Lieberman, D. R.; Simpson, T. R.; McKechney, M. W. J. Am. Chem. Soc. 1997, 119, 994-1004.
    • (1997) J. Am. Chem. Soc. , vol.119 , pp. 994-1004
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    • 27c supporting our assumption of diffusion-controlled quenching
    • 27c supporting our assumption of diffusion-controlled quenching.
  • 49
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    • Tetraethylammonium cyanide was tested as well, but problems arose with the necessary removal of the salt before GC analysis
    • (c) Tetraethylammonium cyanide was tested as well, but problems arose with the necessary removal of the salt before GC analysis.
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    • note
    • This method of measuring IEs is both quantitatively superior to and significantly faster and cheaper than analysis by GC/MS.
  • 51
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    • The choice of 1,3,5-tri-tert-butylbenzene was based on the condition that it absorbs >99% of the incoming light, that its radical cation can oxidize naphthalene (the oxidation potentials of naphthalene and 1,3.5-tri-tert-butylbenzene are 1.60 and 2.01 V, respectively), and that the bulky substituent will decrease the rate of back electron transfer. See: Gould, I. R.; Farid, S. J. Phys. Chem. 1993, 97, 13067-13072.
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    • note
    • -1.
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    • note
    • Evidence for the existence of 1:2 complexes of tetracyanoethene and naphthalene under conditions with a high naphthalene/tetracyanoethene ratio has recently been presented in ref 25.
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    • See ref 27a, pp 287-294
    • See ref 27a, pp 287-294.
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    • note
    • 8 L/mol s (ref 11).
  • 74
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    • A normal equilibrium isotope effect on the electron transfer between an organic radical cation and its neutral parent has recently also been observed for thianthrene: (a) Liu, Z.-L.; Lu, J.-M.; Chen, P.; Wang, X.-L.; Wen, X.-L.; Yang, L.; Liu, Y.-C. J. Chem. Soc., Chem. Commun. 1992, 76-77. (b) Wen, X.-L.; Liu, Z.-L.; Lu, J.-M.; Liu, Y.-C. J. Chem. Soc., Faraday Trans. 1992, 88, 3323-3326.
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    • A normal equilibrium isotope effect on the electron transfer between an organic radical cation and its neutral parent has recently also been observed for thianthrene: (a) Liu, Z.-L.; Lu, J.-M.; Chen, P.; Wang, X.-L.; Wen, X.-L.; Yang, L.; Liu, Y.-C. J. Chem. Soc., Chem. Commun. 1992, 76-77. (b) Wen, X.-L.; Liu, Z.-L.; Lu, J.-M.; Liu, Y.-C. J. Chem. Soc., Faraday Trans. 1992, 88, 3323-3326.
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    • Wen, X.-L.1    Liu, Z.-L.2    Lu, J.-M.3    Liu, Y.-C.4
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    • Attack on the radical cation by the nucleophile in the solvent cage was also proposed by Lemmetyinen and co-workers for the photoamination of phenanthrene in the presence of DCB, on the basis of flash photolysis data: Nieminen, K.; Niiranen, J.; Lemmetyinen, H.; Sychtchikova, I. J. Photochem. Photobiol., A 1991, 61, 235-243.
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    • Padwa, A., Ed.; Marcel Dekker: New York
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    • note
    • This suggests that the diffusing apart of 1,3,5-tri-tert-butylbenzene radical cation and DCB radical anion is more effective than in the corresponding case of naphthalene radical cations; cf. ref 33.


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