Effect of solvent,electronic, and steric factors on the reactivity of 1,1'-diethylferrocene, 1,1'-diacetylferrocene,and 1,1'-bis(diphenylphosphino)ferrocene towards hydrogen peroxide |
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| Authors: | V M Fomin K S Kochetkova M S Galkina |
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| Institution: | 1.Lobachevsky State University,Nizhny Novgorod,Russia |
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| Abstract: | The oxidation of Fc(C2H5)2, Fc(COCH3)2, and Fc(PPh2)2, where Fc is a ferrocene, with hydrogen peroxide in aprotic (dioxane and acetonitrile) and hydroxyl-containing (ethanol, acetonitrile–water, and water) solvents is studied via electron spectroscopy. The reactivity of these metal complexes relative to an oxidant is due to the electron-donor or electron-acceptor properties of substituents, their sizes, and their capability for the specific solvation by a particular solvent. Possible mechanisms of the oxidation of metal complexes are discussed. When Fc(PPh2)2 is oxidized, the formation of ferrocenyl cation Fc+(PPh2)2 is due to the redox isomerism of ferrocenylphosphonium cation Fc(PPh2)P+Ph2, which can form during the reaction between protonated complex Fc(PPh2)P(H+)Ph2 and H2O2. |
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