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Volumn 48, Issue 22, 2009, Pages 10826-10836

LigAnd-Solvent Interactions in a Highly Reduced Metal Chelate Complex: Medium Dependence of the One-Electron Reduction of the bis(Maleonitriledithiolato)Gold Dianion

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EID: 70450163884     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic901547f     Document Type: Article
Times cited : (5)

References (61)
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    • (b) MuellerWesterhoff, U. T.; Vance, B. In Comprehensive Coordination Chemistry; Wilkinson, G., Gillard, R. D., McCleverty, J., Eds.; Pergamon Press: Oxford, 1987; Vol.2, pp 595-631.
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    • An historical perspective on the pertinence of metal dithiolene redox systems to the development of organometallic electrochemistry has appeared. See: Geiger, W. E.
    • An historical perspective on the pertinence of metal dithiolene redox systems to the development of organometallic electrochemistry has appeared. See: Geiger, W. E. Organometallics 2007, 26, 5738.
    • (2007) Organometallics , vol.26 , pp. 5738
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    • 1-/2-/3- couples reported in this paper was consistent with unpublished observations made previously at the University of Vermont by A. Bijunas and one of the present authors.
    • 1-/2-/3- couples reported in this paper was consistent with unpublished observations made previously at the University of Vermont by A. Bijunas and one of the present authors.
    • (1993) J. Chem. Soc., Dalton Trans. , pp. 2267
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    • A fifth (monocationic) member of the gold dithiolene series has been isolated using a (di-tert-butylphenyl)ethylene-dithiolate ligand in place of mnt. See reference 11.
    • A fifth (monocationic) member of the gold dithiolene series has been isolated using a (di-tert-butylphenyl)ethylene-dithiolate ligand in place of mnt. See reference 11.
  • 29
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    • Chemically reversible but electrochemically irreversible ET processes may be generally traced to either a slow ET step (possibly involving a significant structural change), to a reversible coupled chemical reaction, or both.
    • ( 15) Chemically reversible but electrochemically irreversible ET processes may be generally traced to either a slow ET step (possibly involving a significant structural change), to a reversible coupled chemical reaction, or both.
  • 36
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    • note
    • 3- and the CV scan rate.
  • 38
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    • note
    • For double potential step chronoamperometry, see reference 5, pp 207-210. Using step potentials of -0.5 V to -2.0 V and a step time of 300 msec, the ratios of reverse-to-forward currents at different t/r values reproduced those obtained for ferrocene/ferrocenium under identical conditions (e.g., 0.27 at t/z = 2, close to the theoretical value of 0.29). See Supporting Information, Figure S1.
  • 39
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    • -1 experiment for the purpose of lowering the solution resistance. See reference 19.
    • -1 experiment for the purpose of lowering the solution resistance. See reference 19.
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    • s is likely a factor of 2 to 3 larger than the lower estimate reported here, see
    • s is likely a factor of 2 to 3 larger than the lower estimate reported here, (see: Nicholson, R. S. Anal. Chem. 1966, 38, 1406.
    • (1966) Anal. Chem. , vol.38 , pp. 1406
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    • p/2 « 115 mV; α = 0.41).
    • p/2 « 115 mV; α = 0.41).
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    • 24] has an electrochemical "window" from about + 1.4 to -2.3 V vs Ag/AgCl in THF at a glassy carbon electrode.
    • 24] has an electrochemical "window" from about + 1.4 to -2.3 V vs Ag/AgCl in THF at a glassy carbon electrode.
  • 48
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    • This voltammetric behavior places the CE process in the Saveant "KP region" (pure kinetic control), whereas the "KE region" is found in THF (intermediate kinetics). See: John Wiley & Sons: New York
    • This voltammetric behavior places the CE process in the Saveant "KP region" (pure kinetic control), whereas the "KE region" is found in THF (intermediate kinetics). See: Savéant, J.-M. Elements of Molecular and Biomolecular Electrochemistry; John Wiley & Sons: New York, 2006; pp 92-94.
    • (2006) Elements of Molecular and Biomolecular Electrochemistry , pp. 92-94
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    • Bard, A. J., Ed; Marcel Dekker: New York
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    • Evans, D.H.1    In, O.K.M.2
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    • f
    • f;
  • 52
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    • 10 zinc complex, which we find to be optically silent in the 400-800 nm region (see Supporting Information, Figure S7).
    • 10 zinc complex, which we find to be optically silent in the 400-800 nm region (see Supporting Information, Figure S7).
  • 56
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    • 6] when the voltammetry is carried out at a glassy carbon electrode. Some irreversibility and electrode history is observed when a platinum or gold working electrode is employed (A. Bijunas, unpublished work at the University of Vermont).
    • 6] when the voltammetry is carried out at a glassy carbon electrode. Some irreversibility and electrode history is observed when a platinum or gold working electrode is employed (A. Bijunas, unpublished work at the University of Vermont).
  • 57
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    • Five-coordinate Au(I) complexes are rare. See
    • Five-coordinate Au(I) complexes are rare. See: Gimeno, M. C.; Laguna, A. Chem. Rev. 1997, 97, 511.
    • (1997) Chem. Rev. , vol.97 , pp. 511
    • Gimeno, M.C.1    Laguna, A.2


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