Synthesis, Characterization, and Autoreduction of a Highly Electron-Deficient Porphycenatoiron(III) with Trifluoromethyl Substituents

Takashi Hayashi, Yuji Nakashima, Kazuyuki Ito, Takahiro Ikegami, Isao Aritome, Katsuhiro Aoyagi, Tsutomu Ando, Yoshio Hisaeda

Research output: Contribution to journalArticle

26 Citations (Scopus)

Abstract

The synthesis of the first fluorine-containing iron porphycenes, 2,7,12,17-tetraethyl-3,6,13,16-tetrakis(trifluoromethyl)porphycenatoiron(III) chloride [FePc(EtioCF3)]Cl and its μ-oxo dimer [FePc-(EtioCF 3)]2O and their characterizations are reported. The crystal structure of [FePc(EtioCF3)]2O displays a severe saddled distortion of the porphycene framework due to the steric and electronic effects of the CF3 substituents. The oxidation and reduction potentials for then μ-oxo dimer are significantly more positive compared to those observed for the reference μ-oxo dimer of the iron porphycenes and porphyrins having no electron-withdrawing substituent. Moreover, the 1H and 19F NMR spectra of [FePc(EtioCF3)] 2O demonstrated that the μ-oxo dimer is readily converted into the monomeric ferrous complex in pyridine-d5 through autoreduction for 1 day, although the reduction of the reference iron porphycenes and porphyrins are not observed in pyridine. These results indicate that the trifluoromethylated iron porphycene is a highly electron-deficient complex with a pyrrolic macrocycle ligand.

Original languageEnglish
Pages (from-to)7345-7347
Number of pages3
JournalInorganic chemistry
Volume42
Issue number23
DOIs
Publication statusPublished - Nov 17 2003

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Dimers
Iron
dimers
iron
Electrons
Porphyrins
synthesis
porphyrins
pyridines
electrons
Fluorine
fluorine
Chlorides
Crystal structure
chlorides
Nuclear magnetic resonance
Ligands
Oxidation
nuclear magnetic resonance
ligands

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Synthesis, Characterization, and Autoreduction of a Highly Electron-Deficient Porphycenatoiron(III) with Trifluoromethyl Substituents. / Hayashi, Takashi; Nakashima, Yuji; Ito, Kazuyuki; Ikegami, Takahiro; Aritome, Isao; Aoyagi, Katsuhiro; Ando, Tsutomu; Hisaeda, Yoshio.

In: Inorganic chemistry, Vol. 42, No. 23, 17.11.2003, p. 7345-7347.

Research output: Contribution to journalArticle

Hayashi, Takashi ; Nakashima, Yuji ; Ito, Kazuyuki ; Ikegami, Takahiro ; Aritome, Isao ; Aoyagi, Katsuhiro ; Ando, Tsutomu ; Hisaeda, Yoshio. / Synthesis, Characterization, and Autoreduction of a Highly Electron-Deficient Porphycenatoiron(III) with Trifluoromethyl Substituents. In: Inorganic chemistry. 2003 ; Vol. 42, No. 23. pp. 7345-7347.
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