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Volumn 48, Issue 5, 2009, Pages 2156-2165

One-electron oxidation of ruthenocene: Reactions of the ruthenocenium ion in gentle electrolyte media

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EID: 64549102982     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic802105b     Document Type: Article
Times cited : (125)

References (73)
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    • TMS is the standard against which proton NMR chemical shifts are reported
    • TMS is the standard against which proton NMR chemical shifts are reported.
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    • Leading references may be found in (a) Cuffe, L.; Hudson, R. D. A.; Gallagher, J. F.; Jennings, S.; McAdam, C. J.; Connelly, R. B. T.; Manning, A. R.; Robinson, B. H.; Simpson, J. Organometallics 2004, 24, 2051.
    • Leading references may be found in (a) Cuffe, L.; Hudson, R. D. A.; Gallagher, J. F.; Jennings, S.; McAdam, C. J.; Connelly, R. B. T.; Manning, A. R.; Robinson, B. H.; Simpson, J. Organometallics 2004, 24, 2051.
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    • Wilkinson, G, Stone, F. G. A, Abel, E. W, Eds, Pergamon 'Press: Elmsford, NY
    • (a) Bennett, M. A.; Bruce, M. I.; Matheson, T. W. In Comprehensive Organometallic Chemistry; Wilkinson, G., Stone, F. G. A., Abel, E. W., Eds.; Pergamon 'Press: Elmsford, NY, 1982; Vol. 4, pp 759-767.
    • (1982) Comprehensive Organometallic Chemistry , vol.4 , pp. 759-767
    • Bennett, M.A.1    Bruce, M.I.2    Matheson, T.W.3
  • 16
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    • Wilkinson, G, Stone, F. G. A, Abel, E. W, Eds, Pergamon Press: Elmsford. NY
    • (b) Adams, R. D.; Selegue, J. P. In Comprehensive Organometallic Chemistry; Wilkinson, G., Stone, F. G. A., Abel, E. W., Eds.; Pergamon Press: Elmsford. NY, 1982; Vol. 4, pp 1018-1020.
    • (1982) Comprehensive Organometallic Chemistry , vol.4 , pp. 1018-1020
    • Adams, R.D.1    Selegue, J.P.2
  • 35
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    • 2nd ed, Kissinger, P. T, Heineman, W. R, Eds, Marcel Dekker: New York, Chapter 23
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    • (1996) Laboratory Techniques in Electrochemistry
    • Geiger, W.E.1
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    • rev process in which the first one-electron process results in cleavage of the Ru-Ru bond and production of 1 equiv each of ruthenocene and ruthenocenium ion, the second of which would be immediately reduced at the potential of its generation.
    • rev process in which the first one-electron process results in cleavage of the Ru-Ru bond and production of 1 equiv each of ruthenocene and ruthenocenium ion, the second of which would be immediately reduced at the potential of its generation.
  • 43
    • 84869277440 scopus 로고    scopus 로고
    • 1/2 in place of E° values assumes that the activity and diffusion coefficients for Ox and Red are equal in the experimental medium. Under our conditions, potential differences of 10 mV or less are expected.
    • 1/2 in place of E° values assumes that the activity and diffusion coefficients for Ox and Red are equal in the experimental medium. Under our conditions, potential differences of 10 mV or less are expected.
  • 45
    • 64549089576 scopus 로고    scopus 로고
    • Although this value is precisely that expected based on the ionization potential of ruthenocene,21 implying by the earlier reasoning that the dimerization equilibrium constant, Kdim, may be lower when BArF24 is the counteranion, we have no direct confirmation of this
    • 24 is the counteranion, we have no direct confirmation of this.
  • 46
    • 84869277442 scopus 로고    scopus 로고
    • The reversible two-electron oxidation of 5 in CH 2C12/0.1 M [NBu4][ClO4] has been reported in Watanabe, M, Sato, M, Takayama, T. Organometallics 999, 18, 5201 The oxidation product is a fulvalenyl-type isomer of 32, Ru2Cp22(μ2, η6η6-C10H8)]2, We thank Dr. Masaru Sato (Saitama University) for a sample of biruthenocene and Derek Laws (University of Vermont) for determining its potential in WCA media
    • 2+. We thank Dr. Masaru Sato (Saitama University) for a sample of biruthenocene and Derek Laws (University of Vermont) for determining its potential in WCA media.
  • 47
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    • 3 (reference 9) are generally red. See also Borrell, P.; Henderson, E. J. Chem. Soc., Dalton Trans. 1975, 432.
    • 3 (reference 9) are generally red. See also Borrell, P.; Henderson, E. J. Chem. Soc., Dalton Trans. 1975, 432.
  • 48
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    • NMR-line broadening has been well characterized for ferrocene/ferrocenium and for other metallocene redox mixtures. For leading references see (a) Zahl, A, van Eldik, R, Matsumoto, M, Swaddle, T. W. Inorg. Chan. 2003, 42, 3718
    • NMR-line broadening has been well characterized for ferrocene/ferrocenium and for other metallocene redox mixtures. For leading references see (a) Zahl, A.; van Eldik, R.; Matsumoto, M.; Swaddle, T. W. Inorg. Chan. 2003, 42, 3718.
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    • Blümel, 1; Hebendanz, N.; Hudeczek, P.; Köhler, F. H.; Strauss, W. J. Am. Chem. Soc. 1992, 114, 4223.
    • (b) Blümel, 1; Hebendanz, N.; Hudeczek, P.; Köhler, F. H.; Strauss, W. J. Am. Chem. Soc. 1992, 114, 4223.
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    • Watanaba, M.; lwamoto. T.; Hirotoshi, S.; Motoyama, I. J. Organomet. Chem. 1993, 446, 177.
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  • 53
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    • Integrations were earned out on the spectra at 273 K, 253 K, and 228 K by a manual (cut and weigh) method that we estimate to have a relative error of about 10%.
    • Integrations were earned out on the spectra at 273 K, 253 K, and 228 K by a manual (cut and weigh) method that we estimate to have a relative error of about 10%.
  • 68
    • 64549120617 scopus 로고    scopus 로고
    • Although the direct disproportionation of 1+ cannot be ruled out as being responsible for Ru(IV) side products, this is unlikely based on the very unfavorable upper limit of Kdisp (eq 2, Kdisp, 12, 1, 1+]2) that is apparent from the voltammetric data. The fact that the second oxidation of ruthenocene was not observed within the voltammetric window of our measurements assures that E 1/2 for [RuCp2]+/2+ is greater than about 1.7 V vs ferrocene. The Kdisp for ruthenocenium ion in this medium must therefore be less than about 10-22
    • -22.


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