Document Type

Article

Publication Date

2004

Source Publication

Inorganica Chimica Acta

Abstract

The far-infrared spectroelectrochemistry of linear M/Fe/S (M=Mo, W) complexes was investigated in methylene chloride and dichloroethane. With CsI as spectral windows, bands above 200 cm−1 can be observed in methylene chloride, except for a weak methylene chloride band at 450 cm−1. Substitution of dichloroethane for methylene chloride, solvents of nearly identical electrochemical properties, allows one to observe solute bands in the 450-cm−1 region. The far-infrared spectroelectrochemistry of [MoFe2S4Cl4]2− and its tungsten analogue was investigated. The disappearance of the oxidation bands and the appearance of bands due to the reduced product could be clearly observed. The origin of the vibrational bands could be clearly identified using 34S-substituted complexes. In addition to the far-infrared bands, the resonance Raman spectroelectrochemistry of the oxidized and reduced complex, along with the 34S-substituted complexes was obtained. Far-infrared and resonance Raman spectroelectrochemistry can be combined to understand the electrochemical mechanism of transition metal complexes.

The far-infrared spectroelectrochemistry of [MoFe2S4Cl4]2− and its tungsten analogue was investigated. The disappearance of the initial bands and the appearance of bands due to the reduced product could be clearly observed. Resonance Raman spectroscopy and the use of 34S-substituted complexes were used for characterization of the reactant and products.

Comments

Accepted version. Inorganica Chimica Acta, Vol. 357, No. 5, (March, 2004): 1332-1336 DOI: 10.1016/j.ica.2003.11.034 NOTICE: this is the author’s version of a work that was accepted for publication in Inorganica Chimica Acta. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Inorganica Chimica Acta, Vol. 357, No. 5, (March, 2004) DOI: 10.1016/j.ica.2003.11.034

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