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Volumn 122, Issue 23, 2000, Pages 5623-5635

Investigation of dissociative electron transfer mechanisms and reactivity patterns through kinetic amplification by a chain process

Author keywords

[No Author keywords available]

Indexed keywords

2 NITROPROPANATE; 4 NITROBENZALDEHYDE; 4 NITROBENZYL CHLORIDE; CARBON TETRACHLORIDE; HALIDE; NITRO DERIVATIVE; TETRAMETHYLAMMONIUM; UNCLASSIFIED DRUG;

EID: 0034647219     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja000708d     Document Type: Article
Times cited : (39)

References (79)
  • 7
    • 0003279562 scopus 로고
    • RN1 Mechanism
    • The American Chemical Society: Washington, DC
    • RN1 Mechanism. In ACS Monograph 1978; The American Chemical Society: Washington, DC, 1983.
    • (1983) ACS Monograph 1978
    • Rossi, R.A.1    Rossi, R.H.2
  • 10
    • 77956772881 scopus 로고
    • Single Electron Transfer and Nucleophilic Substitution
    • Bethel, D., Ed.; Academic Press: New York
    • (f) Savéant, J.-M. Single Electron Transfer and Nucleophilic Substitution. In Advances in Physical Organic Chemistry; Bethel, D., Ed.; Academic Press: New York, 1990; Vol. 26, pp 1-130.
    • (1990) Advances in Physical Organic Chemistry , vol.26 , pp. 1-130
    • Savéant, J.-M.1
  • 19
    • 0342586204 scopus 로고    scopus 로고
    • note
    • 2m
  • 23
    • 0342586202 scopus 로고    scopus 로고
    • note
    • 6h,i
  • 35
    • 0343891822 scopus 로고    scopus 로고
    • note
    • N2 reaction with its possible bifurcation is satisfactorily described by means of only the two coordinates shown in Figure 3.
  • 43
    • 0342586195 scopus 로고    scopus 로고
    • note
    • (a) With such a fast reaction, the time required for mixing the reactants ceases to be negligible compared to the half-reaction time; 1 min is thus an upper limit.
  • 44
    • 0343891810 scopus 로고    scopus 로고
    • note
    • 14c
  • 46
    • 0342586181 scopus 로고    scopus 로고
    • note
    • -1. Because of Coulombic repulsion, the dimerization of the two anion radicals should be somewhat below the diffusion limit. It follows that the preceding estimate is an upper limit.
  • 48
    • 0342586180 scopus 로고    scopus 로고
    • note
    • RNu→R•+Nu•, respectively. The decrease of the cleavage rate constant from cumyl to benzyl appears to be mainly caused by the increase of the bond dissociation energy in RX, which results from the fact that the tertiary cumyl radical is more stable than the primary benzyl radical. Likewise, the acceleration of the reaction from cumyl to benzyl is mostly a consequence of the increase of the bond dissociation energy in RNu for the same reasons as in RX, plus a destabilizing steric effect in the case of the coupling of the 4-nitrocumyl radical with the 2-nitropropanate ion.
  • 55
    • 0343456071 scopus 로고    scopus 로고
    • note
    • 22b and the difference with unsubstituted benzyl chloride is larger in our case (0.101 vs 0.070 eV). The cause of these discrepancies is likely due to the fact that we used the density functional B3LYP technique both for geometry optimization and energy calculation whereas the AM 1 method was used in ref 22b for geometry optimization and B3LYP with a slightly different basis set energy calculations.
  • 57
    • 0343891799 scopus 로고    scopus 로고
    • note
    • The standard free energy of reaction for the outersphere electron transfer, 0.6 eV, is still positive but much less than in the case of 4-nitropropanate. This is the reason that we have examined only the possibility of an outersphere electron transfer and not that of a dissociative electron transfer from the oximate ion.
  • 64
    • 0343456063 scopus 로고    scopus 로고
    • note
    • 2.
  • 74


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.