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Volumn 114, Issue 19, 2010, Pages 8938-8949

The effect of H-bonding and proton transfer on the voltammetry of 2,3,5,6-tetramethyl-p-phenylenediaminein acetonitrile. An unexpectedly complex mechanism for a simple redox couple

Author keywords

[No Author keywords available]

Indexed keywords

COMPLEX MECHANISMS; ELECTRODE SURFACES; INITIAL SOLUTION; POSITIVE POTENTIAL; PROTONATED STATE; RADICAL CATIONS; REVERSIBLE ELECTRON TRANSFER; SPECTROELECTROCHEMICAL;

EID: 84865723224     PISSN: 19327447     EISSN: 19327455     Source Type: Journal    
DOI: 10.1021/jp100079q     Document Type: Article
Times cited : (28)

References (52)
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    • The Supporting Information of the following paper shows CVs of a number of phenylenediamines in acetonitrile
    • The Supporting Information of the following paper shows CVs of a number of phenylenediamines in acetonitrile. Quinn, J. R.; Foss, F. W.; Venkataraman, L.; Breslow, R. J. Am. Chem. Soc. 2007, 129, 12376-12377.
    • (2007) J. Am. Chem. Soc. , vol.129 , pp. 12376-12377
    • Quinn, J.R.1    Foss, F.W.2    Venkataraman, L.3    Breslow, R.4
  • 22
    • 0003973381 scopus 로고
    • Patai, S.; Rappoport, Z., Ed.; John Wiley & Sons: New York
    • Brown, E. R. In Chemistry of Quinonoid Compounds; Patai, S.; Rappoport, Z., Ed.; John Wiley & Sons: New York, 1988; Vol. 2, pp 1231-1292.
    • (1988) Chemistry of Quinonoid Compounds , vol.2 , pp. 1231-1292
    • Brown, E.R.1
  • 24
    • 84859544196 scopus 로고    scopus 로고
    • 16th ed.; Speight, J. G., Ed.; McGraw-Hill: New York
    • Langes Handbook of Chemistry, 16th ed.; Speight, J. G., Ed.; McGraw-Hill: New York, 2005.
    • (2005) Langes Handbook of Chemistry
  • 41
    • 84885918227 scopus 로고    scopus 로고
    • note
    • a's in Scheme 1) removes the "trap" at the low concentrations, resulting in a simulated CV similar to that seen at higher concentrations. We have extensively explored other possible mechanisms involving only solution-phase chemical steps but have not been able to come up with one that includes all likely reactions and gives, even qualitatively, the observed concentration dependence.
  • 44
    • 49149122068 scopus 로고    scopus 로고
    • Evans, D. H. Chem. Rev. 2008, 108, 2113-2144.
    • (2008) Chem. Rev. , vol.108 , pp. 2113-2144
    • Evans, D.H.1
  • 48
    • 33744456508 scopus 로고    scopus 로고
    • A similar geometry has been reported before for the doubly oxidized form of the completely methylated analogue, N,N,N′,N′-2,3,5,6- octamethylphenylene. In this case, steric hindrance between the C-Me H's and the N-Me H's in the quinoidal state forces the bending. It is also interesting to note that the oxidation of this compound is one of the rare examples of a single 2 e-process in nonaqueous solutions. This is because the intermediate radical state is destabilized more by the steric effects than the fully reduced or fully oxidized forms
    • A similar geometry has been reported before for the doubly oxidized form of the completely methylated analogue, N,N,N′,N′-2,3,5,6- octamethylphenylenediamine. In this case, steric hindrance between the C-Me H's and the N-Me H's in the quinoidal state forces the bending. It is also interesting to note that the oxidation of this compound is one of the rare examples of a single 2 e-process in nonaqueous solutions. This is because the intermediate radical state is destabilized more by the steric effects than the fully reduced or fully oxidized forms. Gruhn, N. E.; Macias-Ruvalcaba, N. A.; Evans, D. H. J. Phys. Chem. A 2006, 110, 5650-5655
    • (2006) J. Phys. Chem. A , vol.110 , pp. 5650-5655
    • Gruhn, N.E.1    Macias-Ruvalcaba, N.A.2    Evans, D.H.3
  • 52
    • 84885923156 scopus 로고    scopus 로고
    • note
    • +.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.