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: Contribution to journalArticle査読

    26 被引用数 (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.

    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
    42
    23
    DOI
    出版ステータス出版済み - 11 17 2003

    All Science Journal Classification (ASJC) codes

    • 物理化学および理論化学
    • 無機化学

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