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Volumn 119, Issue 40, 1997, Pages 9541-9549

Electroreduction of dialkyl peroxides. Activation-driving force relationships and bond dissociation free energies

Author keywords

[No Author keywords available]

Indexed keywords

N,N DIMETHYLFORMAMIDE; PEROXIDE;

EID: 0030730749     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja971416o     Document Type: Article
Times cited : (156)

References (61)
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  • 3
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    • Permanent address: Chemistry Department, Junior College, University of Malta, Msida, Malta
    • Permanent address: Chemistry Department, Junior College, University of Malta, Msida, Malta,
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    • National Research Council of Canada
    • National Research Council of Canada.
  • 5
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    • Maslak, P.1
  • 9
    • 0000497541 scopus 로고
    • See for example: (a) Newton, M. D.; Sutin, N. Annu. Rev. Phys. Chem. 1984, 35, 437. (b) Marcus, R. A.; Sutin, N. Biochem. Biophys. Acta 1985, 577, 265.
    • (1984) Annu. Rev. Phys. Chem. , vol.35 , pp. 437
    • Newton, M.D.1    Sutin, N.2
  • 10
    • 0022004980 scopus 로고
    • See for example: (a) Newton, M. D.; Sutin, N. Annu. Rev. Phys. Chem. 1984, 35, 437. (b) Marcus, R. A.; Sutin, N. Biochem. Biophys. Acta 1985, 577, 265.
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    • Marcus, R.A.1    Sutin, N.2
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    • Bard, A. J., Ed.; Marcel Dekker: New York
    • McCreery, R. L. In Electroanalytical Chemistry, Bard, A. J., Ed.; Marcel Dekker: New York, 1991; Vol. 17, p 221.
    • (1991) Electroanalytical Chemistry , vol.17 , pp. 221
    • McCreery, R.L.1
  • 40
  • 44
    • 9844219578 scopus 로고    scopus 로고
    • note
    • 4 are very similar to each other. In fact, the results obtained at the Hg electrode in the presence of either electrolyte are identical.
  • 46
    • 37049153988 scopus 로고
    • Butler, J. A. V. Trans. Faraday Soc. 1924, 19, 734. Erdey-Gruz, T.; Volmer, M. Z. Phys. Chem. 1930, 150A, 203.
    • (1924) Trans. Faraday Soc. , vol.19 , pp. 734
    • Butler, J.A.V.1
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    • 9844252727 scopus 로고    scopus 로고
    • note
    • Although analogous effects might be caused by improper compensation for the ohmic drop, this possibility was ruled out in our experimental conditions thanks to the parallel experiments that we run using redox couples of known heterogeneous kinetics.
  • 50
    • 9844262653 scopus 로고    scopus 로고
    • note
    • 3 are constants.
  • 51
    • 0001586773 scopus 로고
    • In our previous work (ref 12a) the standard potential was estimated by using the BDFE for decomposition of the neat peroxide. Whereas the BDE of DBF is believed to be solvent independent based on photoacoustic calorimetric studies (Wayner. D. D. M.; Lusztyk, E.; Pagé, D.; Ingold, K. U.; Mulder, P.; Laarhoven, L. J.; Aldrich, H. S. J. Am. Chem. Soc. 1995, 117, 8737), it is not clear that this should be so with the entropy change associated with homolysis. Since the standard potential in eq 22 leads to a BDFE value of 32 kcal/mof (viz. 28 kcal/mo/ from ref 12a) in DMF, we can estimate an entropy contribution to homolysis (-TAS) of 6 kcal/mol in this solvent.
    • (1995) J. Am. Chem. Soc. , vol.117 , pp. 8737
    • Wayner, D.D.M.1    Lusztyk, E.2    Pagé, D.3    Ingold, K.U.4    Mulder, P.5    Laarhoven, L.J.6    Aldrich, H.S.7
  • 52
    • 9844229247 scopus 로고    scopus 로고
    • note
    • a values are about 2-3 units smaller than that of water
  • 60
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    • 12 Whereas halide - ion solvation is symmetrical, in the case of alkoxide ions the negative charge, being concentrated onto the oxygen atom, is not expected to cause significant reorganization of the solvent molecules around the bulky hydrocarbon side of the ion itself. Therefore, an effective radius for the alkoxides was calculated by using once again the above equation, where now AB is the alkoxide and B the oxygen atom.
    • (1969) J. Electroanal. Chem. , vol.20 , pp. 427
    • Peover, M.E.1    Powell, J.S.2
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    • (a) See ref 43b and pertinent references cited therein, (b) Kojima, H.; Bard, A. J. J. Am. Chem. Soc. 1975, 97, 6317.
    • (1975) J. Am. Chem. Soc. , vol.97 , pp. 6317
    • Kojima, H.1    Bard, A.J.2


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.