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Volumn 127, Issue 36, 2005, Pages 12555-12565

19-Electron intermediates and cage-effects in the photochemical disproportionation of [CpW(CO)3]2 with Lewis bases

Author keywords

[No Author keywords available]

Indexed keywords

ELECTRON TRANSITIONS; ELECTRONIC PROPERTIES; INFRARED SPECTROSCOPY; PHOTOCHEMICAL REACTIONS; SOLVENTS;

EID: 24744470709     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja052221g     Document Type: Article
Times cited : (25)

References (70)
  • 1
  • 2
    • 0001209837 scopus 로고
    • Astruc, D. Chem. Rev. 1988, 88, 1189-1216;
    • (1988) Chem. Rev. , vol.88 , pp. 1189-1216
    • Astruc, D.1
  • 29
    • 24744443788 scopus 로고    scopus 로고
    • note
    • -1 (R=Ph).
  • 50
    • 24744436717 scopus 로고    scopus 로고
    • note
    • Errors correspond to 95% confidence intervals. Large errors result from spectral overlap with the 17e radical peak.
  • 51
    • 24744448098 scopus 로고    scopus 로고
    • note
    • Since the disproportionation process consumes 19e species, the 19e dynamics in the first 150 ps might be expected to contain a component which directly corresponds to the disproportionation process. The 19e species, however, is also being formed from the 17e radical on this time scale and so no time component relating to disproportionation is necessarily expected. In addition, spectral overlap with the 17e radical peak prevents accurate analysis of the early time dynamics.
  • 53
    • 24744459131 scopus 로고    scopus 로고
    • note
    • The spectral data between 100 and 800 ps was fit to multiple Gaussian functions and the area of peaks corresponding to the 19e intermediate at multiple time delays were fit to a monoexponential rise, yielding the time constants cited.
  • 56
    • 24744451294 scopus 로고    scopus 로고
    • note
    • - is expected to absorb.
  • 57
    • 24744432172 scopus 로고    scopus 로고
    • note
    • 3.
  • 58
    • 24744432393 scopus 로고    scopus 로고
    • note
    • 3, but it is sufficiently low in amplitude to be masked by the larger decay resulting from 19e formation in these Lewis bases.
  • 59
    • 24744442228 scopus 로고    scopus 로고
    • note
    • Changes in concentration alter diffusion coefficients for solutions, changing the rate of diffusion. For small concentration differences, changes in the diffusion coefficient should be negligible.
  • 62
    • 24744451510 scopus 로고    scopus 로고
    • note
    • To the best of our knowledge, these values have not been published. Initial attempts to determine the reduction potentials of the phosphines suggest that decomposition of the solvent may occur before reduction is achieved; however, more rigorous attempts are called for.
  • 68
    • 24744462181 scopus 로고    scopus 로고
    • note
    • Neglected in Scheme 5 are reactions involving separation of the 17e radicals prior to 19e formation. This scenario likely occurs for cases II and III and to a lesser extent for I. For cases II and III, 17e radical separation prevents disproportionation in the same manner as separation of the 17e and 19e species.
  • 70
    • 24744431527 scopus 로고    scopus 로고
    • note
    • At extremely high concentrations (e.g., with the Lewis base as solvent) the formation of two 19e species within the same solvent cage may hinder disproportionation.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.