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.
本文言語 | 英語 |
---|---|
ページ(範囲) | 7345-7347 |
ページ数 | 3 |
ジャーナル | Inorganic chemistry |
巻 | 42 |
号 | 23 |
DOI | |
出版ステータス | 出版済み - 11月 17 2003 |
!!!All Science Journal Classification (ASJC) codes
- 物理化学および理論化学
- 無機化学