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

doi:10.1021/ja00292a029

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

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

31 Scopus citations

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 E_{p, 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 language	English (US)
Pages (from-to)	1641-1644
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	107
Issue number	6
DOIs	https://doi.org/10.1021/ja00292a029
State	Published - Mar 1985

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@article{08b1ece447334c2aab7c3274d83d5ed8,

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

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.",

author = "Boyd, {David C.} and Bohling, {David A.} and Mann, {Kent R}",

year = "1985",

month = mar,

doi = "10.1021/ja00292a029",

language = "English (US)",

volume = "107",

pages = "1641--1644",

journal = "Journal of the American Chemical Society",

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publisher = "American Chemical Society",

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T1 - Application of the Rotating Photoelectrode to the Detection of an Organotransition-Metal Intermediate. Photoelectrochemical Detection of (η5-C5H5)Fe(CH3CN)3+

AU - Boyd, David C.

AU - Bohling, David A.

AU - Mann, Kent R

PY - 1985/3

Y1 - 1985/3

N2 - 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.

AB - 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.

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