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Volumn 125, Issue 52, 2003, Pages 16300-16309

β-Octafluorocorroles

Author keywords

[No Author keywords available]

Indexed keywords

ABSORPTION SPECTROSCOPY; ALDEHYDES; COMPLEXATION; CONDENSATION; FLUORINE COMPOUNDS; FREE RADICALS; IONIZATION; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; OXIDATION; POSITIVE IONS; REACTION KINETICS; SELF ASSEMBLY; SYNTHESIS (CHEMICAL); X RAY PHOTOELECTRON SPECTROSCOPY;

EID: 0347064292     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja021158h     Document Type: Article
Times cited : (126)

References (51)
  • 2
    • 0346843925 scopus 로고    scopus 로고
    • in press
    • For a minireview on pyrrole-aldehyde condensations viewed as self-assembly processes, see: Ghosh. A. Angew. Chem., Int. Ed., in press.
    • Angew. Chem., Int. Ed.
    • Ghosh, A.1
  • 15
    • 0000694165 scopus 로고    scopus 로고
    • Kadish, K. M., Smith, K. M., Guilard, R., Eds.; Academic Press: San Diego
    • Erben, C.; Will, S.; Kadish, K. M. In The Porphyrin Handbook; Kadish, K. M., Smith, K. M., Guilard, R., Eds.; Academic Press: San Diego, 2000; Vol. 2, p 233.
    • (2000) The Porphyrin Handbook , vol.2 , pp. 233
    • Erben, C.1    Will, S.2    Kadish, K.M.3
  • 19
    • 0141629868 scopus 로고    scopus 로고
    • We should note that with pentafluorobenzaldehyde and 3,4-difluoropyrrole we did not succeed in isolating corrole products under the exact conditions of Gross's solvent-free procedure. Mass spectrometric analysis of the products suggested the presence of a number of expanded porphyrins, although we did not fully characterize these products in this work. As mentioned in the text, Osuka and co-workers have obtained perfluorinated expanded porphyrins from the condensation of pentafluorobenzaldehyde and 3,4-difluoropyrrole under modified Lindsey conditions. However, while this paper was under review, Chang and co-workers reported that increasing the reaction time and temperature in Gross's solvent-free procedure does allow the successful isolation of perfluorinated meso-triphenylcorrole, with pentafluorobenzaldehyde and 3,4-difluoropyrrole as starting materials: Liu, H.-Y.; Lai, T.-S.; Yeung, L.-L. ; Chang, C. K. Org. Lett. 2003, 5, 617-620.
    • (2003) Org. Lett. , vol.5 , pp. 617-620
    • Liu, H.-Y.1    Lai, T.-S.2    Yeung, L.-L.3    Chang, C.K.4
  • 25
    • 79959372471 scopus 로고    scopus 로고
    • Addition/Correction: J. Phys. Chem. B 2002, 106, 5312.
    • (2002) J. Phys. Chem. B , vol.106 , pp. 5312
  • 31
    • 0348104474 scopus 로고    scopus 로고
    • note
    • The ADF program system was obtained from Scientific Computing and Modeling, Department of Theoretical Chemistry, Vrije Universiteit, 1081 HV Amsterdam. The Netherlands. For details of basis sets, grids for numerical integration, etc., the reader is referred to the program manual obtainable from this source.
  • 32
    • 0346843922 scopus 로고    scopus 로고
    • note
    • 19F NMR peaks of the protonated free-base corroles are sensitive to the amount of acid present in the NMR samples. We have not investigated this phenomenon in depth but have empirically found that the sharpest spectra are obtained with only a small drop of added trifluoroacetic acid. Excess acid leads to peak broadening in these spectra.
  • 36
    • 0346213345 scopus 로고    scopus 로고
    • note
    • -1 for Cu β-octabromocorroles.17 We speculate that this vibration has Cβ-Cβ stretching character which would indicate that β-octafluorination and β-octabromination have a comparable bond-lengthening influence on the Cβ-Cβ bonds. Because β-octafluorination and β-octabromination may be expected to induce different degrees of nonplanarity on the corrole ring, the similarity of this frequency for the two classes of halogenated copper corroles may indicate that the halogenation-induced downshift of this vibration reflects a direct bond-lengthening effect of the β-halogen substituents on the Cβ-Cβ bonds rather than a nonplanarity effect.
  • 38
    • 0002724520 scopus 로고    scopus 로고
    • Kadish, K. M., Smith, K. M., Guilard, R., Eds.; Academic Press: San Diego
    • Walker, F. A. In The Porhyrin Handbook: Kadish, K. M., Smith, K. M., Guilard, R., Eds.; Academic Press: San Diego. 2000: Vol. 5. p 81.
    • (2000) The Porhyrin Handbook , vol.5 , pp. 81
    • Walker, F.A.1
  • 45
    • 0037305747 scopus 로고    scopus 로고
    • It should be noted that the PW91 functional used by us and the B3LYP functional used in ref 21 give qualitatively similar but, quantitatively, significantly different spin populations for FeCl corroles. In the absence of higher-level calculations of these results, we cannot say whether PW91 or B3LYP provide a better description of reality. For a review of calibration of PW91 and B3LYP calculations on biologically relevant transition metal complexes against CASPT2 and CCSD(T) calculations, see: Ghosh, A.; Taylor, P. R. Curr. Opin. Chem. Biol. 2003, 7, 113.
    • (2003) Curr. Opin. Chem. Biol. , vol.7 , pp. 113
    • Ghosh, A.1    Taylor, P.R.2
  • 46
    • 0005665165 scopus 로고
    • In an early DFT study (Ghosh, A. J. Am. Chem. Soc. 1995, 117, 4691) of porphyrins, one of us noted that meso- and β-halogen substituents exert quite different electronic effects. In particular, meso-halogen substituents strongly stabilize porphyrin A2u radicals, presumably by absorbing some spin density from the meso positions. A similar situation might be operative for meso-fluorinated corroles, which are unknown so far.
    • (1995) J. Am. Chem. Soc. , vol.117 , pp. 4691
    • Ghosh, A.1


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