Application of the Rotating Photoelectrode to the Detection of an Organotransition-Metal Intermediate. Photoelectrochemical Detection of (η5-C5H5)Fe(CH3CN)3+

David C. Boyd, David A. Bohling, Kent R. Mann

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Abstract

Photolysis of CpFe(η6-p-xyl)+(p-xyl = p-xylene) in acetonitrile at-40 °C results in an intensely purple solution that contains the CpFe(CH3CN)3ion. Allowing this purple solution to warm to room temperature results in the formation of the previously reported photoproducts: ferrocene and Fe(CH3CN)62+. The cyclic voltammogram of CpFe(CH3CN)3+ exhibits one irreversible oxidation Ep, a= +0.64 V vs. Ag/AgCl which is cyclopentadienyl ligand centered. Anodic photocurrents due to the CpFe(CH3CN)3+ cation were detected at room temperature via the photolysis of acetonitrile solutions of CpFe(η6-arene)+(arene = p-xylene, 9-cinnamylidenefluorene) through a rotating photoelectrode (RPE). A decrease in the photocurrent with increased rate of RPE rotation is observed for arene = 9-cinnamylidenefluorene, but for arene = p-xylene, the photocurrent was independent of rotation rate. These observations are explained in terms of the differences in the molar absorptivity of the two compounds.

Original languageEnglish (US)
Pages (from-to)1641-1644
Number of pages4
JournalJournal of the American Chemical Society
Volume107
Issue number6
DOIs
StatePublished - Mar 1985

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