Ruthenocene-Type Complexes of N-Fused Porphyrins
| Autor: | Ayumi Sato, Hiroyuki Furuta, Motoki Toganoh, Hideaki Matsuo |
|---|---|
| Rok vydání: | 2016 |
| Předmět: |
Magnetic Resonance Spectroscopy
Porphyrins Nitrogen Stereochemistry Molecular Conformation chemistry.chemical_element Crystallography X-Ray 010402 general chemistry 01 natural sciences Catalysis chemistry.chemical_compound Cyclopentadienyl complex Coordination Complexes Organometallic Compounds Ruthenocene Moiety HOMO/LUMO 010405 organic chemistry Ligand Organic Chemistry Electrochemical Techniques General Chemistry Porphyrin 0104 chemical sciences Ruthenium Crystallography chemistry Quantum Theory Spectrophotometry Ultraviolet Metallocene |
| Zdroj: | Chemistry - A European Journal. 22:8316-8322 |
| ISSN: | 0947-6539 |
| DOI: | 10.1002/chem.201600813 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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