Ruthenocene-Type Complexes of N-Fused Porphyrins

Motoki Toganoh, Hideaki Matsuo, Ayumi Sato, Hiroyuki Furuta

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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 - Jan 1 2016

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Porphyrins
Ligands
Ruthenium
X ray crystallography
Discrete Fourier transforms
Nuclear magnetic resonance
Spectroscopy
ruthenocene

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Ruthenocene-Type Complexes of N-Fused Porphyrins. / Toganoh, Motoki; Matsuo, Hideaki; Sato, Ayumi; Furuta, Hiroyuki.

In: Chemistry - A European Journal, Vol. 22, No. 24, 01.01.2016, p. 8316-8322.

Research output: Contribution to journalArticle

Toganoh, Motoki ; Matsuo, Hideaki ; Sato, Ayumi ; Furuta, Hiroyuki. / Ruthenocene-Type Complexes of N-Fused Porphyrins. In: Chemistry - A European Journal. 2016 ; Vol. 22, No. 24. pp. 8316-8322.
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