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

研究成果: ジャーナルへの寄稿記事

26 引用 (Scopus)

抄録

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.

元の言語英語
ページ(範囲)7345-7347
ページ数3
ジャーナルInorganic chemistry
42
発行部数23
DOI
出版物ステータス出版済み - 11 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

これを引用

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.

:: Inorganic chemistry, 巻 42, 番号 23, 17.11.2003, p. 7345-7347.

研究成果: ジャーナルへの寄稿記事

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. :: Inorganic chemistry. 2003 ; 巻 42, 番号 23. pp. 7345-7347.
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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.",
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T1 - Synthesis, Characterization, and Autoreduction of a Highly Electron-Deficient Porphycenatoiron(III) with Trifluoromethyl Substituents

AU - Hayashi, Takashi

AU - Nakashima, Yuji

AU - Ito, Kazuyuki

AU - Ikegami, Takahiro

AU - Aritome, Isao

AU - Aoyagi, Katsuhiro

AU - Ando, Tsutomu

AU - Hisaeda, Yoshio

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AB - 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.

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