Ruthenocene-Type Complexes of N-Fused Porphyrins

Motoki Toganoh, Hideaki Matsuo, Ayumi Sato, Hiroyuki Furuta

    Research output: Contribution to journalArticlepeer-review

    15 Citations (Scopus)

    Abstract

    Ruthenocene-type hybrid complexes with N-fused porphyrinato ligands, [Ru(NFp)Cp] (NFp=N-fused porphyrin, Cp=cyclopentadienyl), have been prepared and characterized by NMR and UV/Vis/NIR spectroscopy, cyclovoltammetry, and X-ray crystallography. [Ru(NFp)Cp] is a common low-spin ruthenium(II) complex and shows strong aromaticity. The Ru-Cp distance (1.833 Å) in [Ru(NFp)Cp] is comparable to that in [RuCp2] (1.840 Å). DFT calculations on [Ru(NFp)Cp] showed the unequivocal contribution of the RuCp moiety as well as the NFp moiety to both the HOMO and LUMO, constructing a three-dimensional d-π conjugated system. The HOMO-LUMO gaps of [Ru(NFp)Cp] are insensitive to the substituents on the NFp ligand, which is illustrated spectroscopically as well as theoretically. This is in sharp contrast to the ligand precursor, the N-fused porphyrin, in which the HOMO-LUMO gap is affected by substituents in a similar manner to standard porphyrins and related macrocycles.

    Original languageEnglish
    Pages (from-to)8316-8322
    Number of pages7
    JournalChemistry - A European Journal
    Volume22
    Issue number24
    DOIs
    Publication statusPublished - Jun 6 2016

    All Science Journal Classification (ASJC) codes

    • Catalysis
    • Organic Chemistry

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