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 |
| 巻 | 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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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
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TY - JOUR
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
PY - 2003/11/17
Y1 - 2003/11/17
N2 - 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.
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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U2 - 10.1021/ic034757d
DO - 10.1021/ic034757d
M3 - Article
C2 - 14606820
AN - SCOPUS:0242693881
VL - 42
SP - 7345
EP - 7347
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 23
ER -