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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.
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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.
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32
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0346843922
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note
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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.
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33
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note
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-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.
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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.
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