Tetra(pentafluorophenyl)porpholactone

Martin Gouterman, Robert J. Hall, Gamal Eddin Khalil, Paul C. Martin, Eric G. Shankland, Ronald Cerny

Research output: Contribution to journalArticle

93 Citations (Scopus)

Abstract

Tetra(Pentafluorophenyl)porphyrin [H2.(TFPP)] in refluxing acetic acid with AgNO3 converts to tetrafpenta- fluorophenyl)porpholactone, I; i.e. one exo C2H2 unit becomes CO2. This change is proven by mass spectrometry and supported by 1H NMR, 19F NMR, and FTIR. I has a porphyrinic absorption spectrum and a strong fluorescence, with a quantum yield of 0.2. Addition of oxalic acid allows reproducible conversion of H2(TFPP)→I, and a 15% yield has been obtained. Iterative extended Hückel (IEH) calculations confirm a porphyrinic electronic structure with the π orbitals on both the oxa and oxo oxygen present in three of the porphyrin “four orbitals'1responsible for the optical spectra. Under similar conditions another metal-free porphyrinic substance has been made, which is tentatively identified as a porphodilactone. Also Ag, Ni, and Cu derivatives have been made that are presumed to be porpholactones or porphodilactones. IEH calculations predict that in the free bases the central protons are trans, avoiding the azlactone ring in the porpholactone and the opposite porphodilactone; in the adjacent porphodilactone, they are also predicted to be trans rather than cis.

Original languageEnglish (US)
Pages (from-to)3702-3707
Number of pages6
JournalJournal of the American Chemical Society
Volume111
Issue number10
DOIs
StatePublished - May 1989

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Oxalic Acid
Porphyrins
Fourier Transform Infrared Spectroscopy
Acetic Acid
Protons
Mass Spectrometry
Fluorescence
Metals
Nuclear magnetic resonance
Oxygen
Oxalic acid
Quantum yield
Acetic acid
Electronic structure
Mass spectrometry
Absorption spectra
Derivatives
2,2,3,3-tetrafluoroputrescine
Proton Magnetic Resonance Spectroscopy
meso-tetra(pentafluorophenyl)porphyrin

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Gouterman, M., Hall, R. J., Khalil, G. E., Martin, P. C., Shankland, E. G., & Cerny, R. (1989). Tetra(pentafluorophenyl)porpholactone. Journal of the American Chemical Society, 111(10), 3702-3707. https://doi.org/10.1021/ja00192a030

Tetra(pentafluorophenyl)porpholactone. / Gouterman, Martin; Hall, Robert J.; Khalil, Gamal Eddin; Martin, Paul C.; Shankland, Eric G.; Cerny, Ronald.

In: Journal of the American Chemical Society, Vol. 111, No. 10, 05.1989, p. 3702-3707.

Research output: Contribution to journalArticle

Gouterman, M, Hall, RJ, Khalil, GE, Martin, PC, Shankland, EG & Cerny, R 1989, 'Tetra(pentafluorophenyl)porpholactone', Journal of the American Chemical Society, vol. 111, no. 10, pp. 3702-3707. https://doi.org/10.1021/ja00192a030
Gouterman M, Hall RJ, Khalil GE, Martin PC, Shankland EG, Cerny R. Tetra(pentafluorophenyl)porpholactone. Journal of the American Chemical Society. 1989 May;111(10):3702-3707. https://doi.org/10.1021/ja00192a030
Gouterman, Martin ; Hall, Robert J. ; Khalil, Gamal Eddin ; Martin, Paul C. ; Shankland, Eric G. ; Cerny, Ronald. / Tetra(pentafluorophenyl)porpholactone. In: Journal of the American Chemical Society. 1989 ; Vol. 111, No. 10. pp. 3702-3707.
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