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Volumn 74, Issue 12, 2009, Pages 4472-4478

Establishment of the C-NO bond dissociation energy scale in solution and its application in analyzing the trend of NO transfer from C-nitroso compound to thiols

Author keywords

[No Author keywords available]

Indexed keywords

ACETONITRILE SOLUTIONS; BOND DISSOCIATION ENERGIES; C-NITROSO COMPOUNDS; CHEMICAL EQUATIONS; DIRECT TITRATION; ELECTRODE POTENTIALS; GASPHASE; HETEROLYTIC DISSOCIATION; HOMOLYTIC BONDS; NITROSO; THERMODYNAMIC CYCLE; THERMODYNAMIC PARAMETER;

EID: 67249141126     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo900732b     Document Type: Article
Times cited : (9)

References (83)
  • 50
    • 67249152228 scopus 로고    scopus 로고
    • note
    • The model compounds studied in this work are all tertiary C-nitroso molecules with both sterically bulky and electron-withdrawing groups, which are significantly disfavored for dimerization in solution. Furthermore, the concentration of the C-nitroso compounds under the calorimetric titration conditions is very low (<0.005 M), so conjugation of the C-nitroso species in solution is negligible. Therefore the contribution from the ΔG of dimerization could be neglected without scarifying accuracy. In a recent report by Toone et al., an approximate range of ca.-0.5 to +2.2 kcal/mol for the ΔG of dimerization of R-cyano C-nitroso compound at 1 M concentration at 25°C was predicted (see ref 6b).
  • 51
    • 67249165224 scopus 로고    scopus 로고
    • note
    • rxn (eq 2, Scheme 2). The latter can be directly determined by titration calorimetry for fast and quantitative reactions as in the present practice.
  • 52
    • 0001634401 scopus 로고
    • Arnett has shown that the temperature dependence of the redox processes for resonance-delocalized anions and for the reversible cation-to-radical conversions was experimentally observed to be negligible. Then the corresponding entropy changes for redox processes should be insignificant. For previous validation of similar treatment, see
    • Arnett has shown that the temperature dependence of the redox processes for resonance-delocalized anions and for the reversible cation-to-radical conversions was experimentally observed to be negligible. Then the corresponding entropy changes for redox processes should be insignificant. For previous validation of similar treatment, see: (a) Arnett, E. M.; Amarnath, K.; Harvey, N. G.; Cheng, J.-P. Science 1990, 247, 423.
    • (1990) Science , vol.247 , pp. 423
    • Arnett, E.M.1    Amarnath, K.2    Harvey, N.G.3    Cheng, J.-P.4
  • 67
    • 67249093170 scopus 로고    scopus 로고
    • note
    • In this paper, all of the calculations were done with Gaussian 98.23 The geometry was optimized by using B3LYP/6-31G*, with each optimized structure verified by B3LYP/6-31G* frequency calculations as a real minimum without any imaginary frequency.
  • 78
    • 0001116519 scopus 로고    scopus 로고
    • a term is to convert the equilibrium acidity from pK unit to kcal/mol. The application of this expression widely appears in the study of acidity equilibrium. See ref 20 and
    • a term is to convert the equilibrium acidity from pK unit to kcal/mol. The application of this expression widely appears in the study of acidity equilibrium. See ref 20 and: (a) Cheng, J. P.; Liu, B.; Zhang, X. J. Org. Chem. 1998, 63, 7574.
    • (1998) J. Org. Chem. , vol.63 , pp. 7574
    • Cheng, J.P.1    Liu, B.2    Zhang, X.3
  • 82
    • 67249159560 scopus 로고    scopus 로고
    • note
    • eq) of NO transfer between NNP and different thiols can then be determined from the calculated concentrations as shown in eq 6 in Scheme 6.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.