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Volumn 110, Issue 17, 2006, Pages 5874-5886

Quantum-chemical predictions of redox potentials of organic anions in dimethyl sulfoxide and reevaluation of bond dissociation enthalpies measured by the electrochemical methods

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL BONDS; COMPUTATIONAL METHODS; DISSOCIATION; ELECTROCHEMISTRY; ENTHALPY; ORGANIC COMPOUNDS; REDOX REACTIONS; SOLVENTS;

EID: 33744479736     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp055682x     Document Type: Article
Times cited : (65)

References (116)
  • 64
    • 17144470177 scopus 로고    scopus 로고
    • (h) Namazian, M. THEOCHEM 2003, 664-665, 273.
    • (2003) THEOCHEM , vol.664-665 , pp. 273
    • Namazian, M.1
  • 99
    • 0344887064 scopus 로고
    • and references therein
    • Bordwell, F. G. Acc. Chem. Res. 1988, 21, 456 and references therein.
    • (1988) Acc. Chem. Res. , vol.21 , pp. 456
    • Bordwell, F.G.1
  • 100
    • 33744459621 scopus 로고    scopus 로고
    • note
    • In calculating the entropy change, one needs to include an extra term (-RT In4 = -0.04 eV) in addition to the standard thermal entropy terms. This term corresponds to the entropic contribution from the electronic spin degeneracy.
  • 109
    • 33744496418 scopus 로고    scopus 로고
    • note
    • (b) It is worth noting that the Bell model of solvation is only approximately correct. A more accurate description of the solvation requires the knowledge of detailed local charge distributions.
  • 110
    • 33744468103 scopus 로고    scopus 로고
    • note
    • A number of previous studies have criticized the use of electro-chemical methods to measure BDEs by emphasizing the neglect of solvent effects, particularly hydrogen bonding. (For examples, see:
  • 113
    • 0037130675 scopus 로고    scopus 로고
    • (c) Pratt, D. A.; DiLabio, G. A.; Valgimigli, L.; Pedulli, G. F.; Ingold, K. U. J. Am. Chem. Soc. 2002, 124, 11085.) However, if we keep in mind that the experimental BDE values have an intrinsic error bar of about 2-3 kcal/mol, most of the previous debated problems can actually be attributed to unavoidable experimental errors. What we are emphasizing here are those BDE values which may be wrong by over 5 kcal/mol.
    • (2002) J. Am. Chem. Soc. , vol.124 , pp. 11085
    • Pratt, D.A.1    DiLabio, G.A.2    Valgimigli, L.3    Pedulli, G.F.4    Ingold, K.U.5


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.