Facile Synthesis of meso-Tetrakis(perfluoroalkyl)porphyrins: Spectroscopic Properties and X-ray Crystal Structure of Highly Electron-Deficient 5,10,15,20-Tetrakis(heptafluoropropyl)porphyrin

Stephen G. DiMagno, R. Allen Williams, Michael J. Therien

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Abstract

The synthesis, structure, optical spectrum, and electrochemistry of 5,10,15,20-tetrakis(perfluoropropyl)porphyrin, 1, are reported. The high yield preparative method, starting from (hydroxymethyl)pyrrole precursors such as 2,2,3,3,4,4,4-heptafluoro-1-(2-pyrrolyl)-1-butanol, 2, is general for a wide variety of meso-perfluoroalkyl-substituted porphyrins. The X-ray crystal structure of 1 is noteworthy in that it shows a S4-distorted porphyrin core that appears to derive from an unusual hydrogen bonding interaction between a fluorocarbon fluorine atom and a porphyrin NH proton. A comparison of the electrochemical properties of the zinc derivative of 1 with those of [5,10,15,20-tetrakis(pentafluorophenyl)-2,3,7,8,12,13,17,18-octabromoporphinato]zinc(II) indicates that meso-perfluoroalkylated porphyrins are among the most electron-deficient porphyrin ligands known. meso-Tetrakis(perfluoroalkyl)porphyrins and their elaborated derivatives, with their unusual electronic properties, should thus serve as useful ligands for a variety of catalytic and stoichiometric transition metal-mediated redox reactions.

Original languageEnglish (US)
Pages (from-to)6943-6948
Number of pages6
JournalJournal of Organic Chemistry
Volume59
Issue number23
DOIs
StatePublished - Nov 1 1994

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Porphyrins
Crystal structure
X rays
Electrons
Zinc
Ligands
Derivatives
Fluorocarbons
1-Butanol
Pyrroles
Fluorine
Redox reactions
Electrochemistry
Electrochemical properties
Electronic properties
Transition metals
Protons
Hydrogen bonds
Atoms

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Facile Synthesis of meso-Tetrakis(perfluoroalkyl)porphyrins : Spectroscopic Properties and X-ray Crystal Structure of Highly Electron-Deficient 5,10,15,20-Tetrakis(heptafluoropropyl)porphyrin. / DiMagno, Stephen G.; Williams, R. Allen; Therien, Michael J.

In: Journal of Organic Chemistry, Vol. 59, No. 23, 01.11.1994, p. 6943-6948.

Research output: Contribution to journalArticle

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abstract = "The synthesis, structure, optical spectrum, and electrochemistry of 5,10,15,20-tetrakis(perfluoropropyl)porphyrin, 1, are reported. The high yield preparative method, starting from (hydroxymethyl)pyrrole precursors such as 2,2,3,3,4,4,4-heptafluoro-1-(2-pyrrolyl)-1-butanol, 2, is general for a wide variety of meso-perfluoroalkyl-substituted porphyrins. The X-ray crystal structure of 1 is noteworthy in that it shows a S4-distorted porphyrin core that appears to derive from an unusual hydrogen bonding interaction between a fluorocarbon fluorine atom and a porphyrin NH proton. A comparison of the electrochemical properties of the zinc derivative of 1 with those of [5,10,15,20-tetrakis(pentafluorophenyl)-2,3,7,8,12,13,17,18-octabromoporphinato]zinc(II) indicates that meso-perfluoroalkylated porphyrins are among the most electron-deficient porphyrin ligands known. meso-Tetrakis(perfluoroalkyl)porphyrins and their elaborated derivatives, with their unusual electronic properties, should thus serve as useful ligands for a variety of catalytic and stoichiometric transition metal-mediated redox reactions.",
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AB - The synthesis, structure, optical spectrum, and electrochemistry of 5,10,15,20-tetrakis(perfluoropropyl)porphyrin, 1, are reported. The high yield preparative method, starting from (hydroxymethyl)pyrrole precursors such as 2,2,3,3,4,4,4-heptafluoro-1-(2-pyrrolyl)-1-butanol, 2, is general for a wide variety of meso-perfluoroalkyl-substituted porphyrins. The X-ray crystal structure of 1 is noteworthy in that it shows a S4-distorted porphyrin core that appears to derive from an unusual hydrogen bonding interaction between a fluorocarbon fluorine atom and a porphyrin NH proton. A comparison of the electrochemical properties of the zinc derivative of 1 with those of [5,10,15,20-tetrakis(pentafluorophenyl)-2,3,7,8,12,13,17,18-octabromoporphinato]zinc(II) indicates that meso-perfluoroalkylated porphyrins are among the most electron-deficient porphyrin ligands known. meso-Tetrakis(perfluoroalkyl)porphyrins and their elaborated derivatives, with their unusual electronic properties, should thus serve as useful ligands for a variety of catalytic and stoichiometric transition metal-mediated redox reactions.

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