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Iron–xanthate complexes [Fe(CO)<sub>2</sub>(η-C<sub>5</sub>R<sub>5</sub>){SC(S)OEt}] and [Fe(CO)(η-C<sub>5</sub>R<sub>5</sub>)(S<sub>2</sub>COEt)](R = H or Me). Synthesis and electrochemistry
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1988
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Inorganic ChemistryChemical EngineeringEngineeringCoordination ComplexOrganometallic ElectrochemistryXanthate ComplexesOrganometallic CatalysisCatalysisMolecular ComplexChemistryMonocarbonyl ComplexesInorganic SynthesisElectrochemistryCarbon MonoxideInorganic Compound
Xanthate complexes of the type [Fe(CO)2(η-C5R5){SC(S)OEt}][R = H (1) or Me (2)] can be conveniently prepared by reaction between [{Fe(CO)2(η-C5R5)}] and [SC(S)OEt]2 in cyclohexane. U.v. photolysis of (1) and (2) causes decarbonylation and affords the chelate complexes [Fe(CO)(η-C5R5)(S2COEt)][R = H (3) or Me (4)]. The electrochemical behaviour of these complexes has been studied both in acetonitrile and dichloromethane using cyclic voltammetry and coulometry. The monocarbonyl complexes (3) and (4) in dichloromethane exhibit a reversible oxidation–reduction process. In acetonitrile the oxidation reaction is accompanied by the co-ordination of solvent. The multicyclic voltammograms of the dicarbonyl complexes (1) and (2), in both solvents, reveal that the oxidation is followed by elimination of one molecule of carbon monoxide from iron, affording the corresponding chelate complexes (3) and (4).