Syntheses and characterizations of a new valence-averaged mixed-valence diiron complex and a carbonyl derivative of the isovalent diiron complex
The synthesis and characterization of a new mixed-valence bimetallic iron complex [Fe2(C20H36N8)(Cl)4]+ are reported. This binuclear species is assigned as a Robin and Day strongly coupled Class III mixed-valence species based on infrared spectroscopy, cyclic voltammetry, electronic spectroscopy, an...
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| Format: | Others |
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Scholarly Commons
1995
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| Online Access: | https://scholarlycommons.pacific.edu/uop_etds/2292 https://scholarlycommons.pacific.edu/cgi/viewcontent.cgi?article=3291&context=uop_etds |
| Summary: | The synthesis and characterization of a new mixed-valence bimetallic iron complex [Fe2(C20H36N8)(Cl)4]+ are reported. This binuclear species is assigned as a Robin and Day strongly coupled Class III mixed-valence species based on infrared spectroscopy, cyclic voltammetry, electronic spectroscopy, and X-ray photoelectron spectroscopy. The mixed-valence compound exhibits an intense NIR band at 883 nm with a molar absorptivity of 18000 M-1cm-1 and a band width at half-intensity of 2181 cm-1. This NIR band position Is solvent independent and HAM is calculated to be 5660 cm-1. A comproportionation constant of 1.7 x 1013 is obtained and this large value indicates that the mixed-valence species is stabilized by delocalization. The XPS results of the mixed-valence compound for the binding energies from Fe 2p3/2 region show only a single peak, indicating the unpaired electron is delocalized on the short time scale (10-17 sec) of XPS measurement.
Also a carbonyl derivative of the dimacrocycle bimetallic complex [Fe2(C20H36N8)(Cl)4]4+ has been isolated and its IR spectrum, electronic spectrum and electrochemical properties have been investigated. |
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