Tetra(pentafluorophenyl)porpholactone

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

doi:10.1021/ja00192a030

Tetra(pentafluorophenyl)porpholactone

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

Research output: Contribution to journal › Article › peer-review

99 Scopus citations

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 language	English (US)
Pages (from-to)	3702-3707
Number of pages	6
Journal	Journal of the American Chemical Society
Volume	111
Issue number	10
DOIs	https://doi.org/10.1021/ja00192a030
State	Published - May 1989

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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title = "Tetra(pentafluorophenyl)porpholactone",

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 H{\"u}ckel (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.",

author = "Martin Gouterman and Hall, {Robert J.} and Khalil, {Gamal Eddin} and Martin, {Paul C.} and Shankland, {Eric G.} and Cerny, {Ronald L.}",

year = "1989",

month = may,

doi = "10.1021/ja00192a030",

language = "English (US)",

volume = "111",

pages = "3702--3707",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "10",

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TY - JOUR

T1 - Tetra(pentafluorophenyl)porpholactone

AU - Gouterman, Martin

AU - Hall, Robert J.

AU - Khalil, Gamal Eddin

AU - Martin, Paul C.

AU - Shankland, Eric G.

AU - Cerny, Ronald L.

PY - 1989/5

Y1 - 1989/5

N2 - 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.

AB - 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.

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