Synthesis and reactivity of new heterodinuclear iron/rhenium Cx complexes of the formula (η-C5Me5)Re(NO)(PPh3)(CC)n(η-dppe)Fe(η-C5Me5) (n = 3, 4): Redox properties and a dicobalt hexacarbonyl adduct |
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Authors: | Slawomir Szafert Frdric Paul Wayne E Meyer John A Gladysz Claude Lapinte |
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Institution: | Slawomir Szafert, Frédéric Paul, Wayne E. Meyer, John A. Gladysz,Claude Lapinte, |
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Abstract: | We report in this communication the synthesis and characterization of two Fe/Re heterodinuclear complexes 3n of formula (η5-C5Me5)Re(NO)(PPh3)(CC)n(η2-dppe)Fe(η5-C5Me5) (n = 3, 4) as well as the hexacarbonyl dicobalt adduct (4) of the hexatriynediyl complex 33. We show by cyclic voltammetry that the “electronic communication” between the organometallic endgroups and thereby the thermodynamic stability of the corresponding mixed-valent (MV) parent 3n+ is strongly influenced by bridge extension or by complexation of the Co2(CO)6] fragment. In the case of the hexatriynediyl complex, the MV complex 33+ or 4 can be isolated by performing the chemical oxidation of 33 at low temperature. Spectroscopic studies of this compound and of other stable oxidized redox congeners should now help us to unravel how bridge extension modifies the electronic communication between the different redox-active endgroups in this family of unsymmetrically-substituted polyynediyl compounds. |
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Keywords: | Dimetalla-polyyne Iron/rhenium-complexes Dicobalthexacarbonyl-adduct Synthesis Cyclic voltammetryMots-clé s: Polyyne dimé tallé Complexes fer/rhé nium Adduit dicobalthexacarbonyle Synthè se Voltamé trie cyclique |
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