In situ electrochemical-ATR-FTIR spectroscopic studies on solution phase 2,4,6-tri-substituted phenoxyl radicals

Richard D. Webster

doi:10.1016/S1388-2481(02)00517-9

In situ electrochemical-ATR-FTIR spectroscopic studies on solution phase 2,4,6-tri-substituted phenoxyl radicals

Richard D. Webster^*

^*Corresponding author for this work

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

26 Citations (Scopus)

Abstract

2,4,6-Tri-tert-butylphenolate and 2,6-di-tert-butyl-4- methoxyphenolate (prepared by reacting the corresponding phenols with dry Et₄NOH) were oxidised by one-electron in CH₃CN at room temperature (with 0.2 M Bu₄NPF₆ as the supporting electrolyte) in a controlled potential electrolysis cell at negative potentials (-0.68 to -0.84 V vs. Fc/Fc⁺ (Fc = ferrocene)) to produce moderately stable phenoxyl radicals. The oxidation reaction was monitored using in situ FTIR spectroscopy between 1800-1000 cm^-1 with an attenuated total reflectance (ATR) probe containing a diamond composite sensor inserted into the working electrode compartment of the electrolysis cell. Analysis of the data obtained during the chemically reversible oxidation of the phenolate anions allowed the identification of several IR absorption bands that could be assigned to the phenoxyl radicals with notable bands observed at 1592-1573 cm^-1 and 1505-1509 cm^-1 that were assigned to the ν_8a(C_oC_m ring stretch) and ν_7a(C_a-O^. stretch) modes, respectively.

Original language	English
Pages (from-to)	6-11
Number of pages	6
Journal	Electrochemistry Communications
Volume	5
Issue number	1
DOIs	https://doi.org/10.1016/S1388-2481(02)00517-9
Publication status	Published - 1 Jan 2003

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title = "In situ electrochemical-ATR-FTIR spectroscopic studies on solution phase 2,4,6-tri-substituted phenoxyl radicals",

abstract = "2,4,6-Tri-tert-butylphenolate and 2,6-di-tert-butyl-4- methoxyphenolate (prepared by reacting the corresponding phenols with dry Et4NOH) were oxidised by one-electron in CH3CN at room temperature (with 0.2 M Bu4NPF6 as the supporting electrolyte) in a controlled potential electrolysis cell at negative potentials (-0.68 to -0.84 V vs. Fc/Fc+ (Fc = ferrocene)) to produce moderately stable phenoxyl radicals. The oxidation reaction was monitored using in situ FTIR spectroscopy between 1800-1000 cm-1 with an attenuated total reflectance (ATR) probe containing a diamond composite sensor inserted into the working electrode compartment of the electrolysis cell. Analysis of the data obtained during the chemically reversible oxidation of the phenolate anions allowed the identification of several IR absorption bands that could be assigned to the phenoxyl radicals with notable bands observed at 1592-1573 cm-1 and 1505-1509 cm-1 that were assigned to the ν8a(CoCm ring stretch) and ν7a(Ca-O. stretch) modes, respectively.",

keywords = "Attenuated total reflectance, FTIR spectroscopy, Phenol, Phenolate anion, Phenoxyl radical",

author = "Webster, {Richard D.}",

year = "2003",

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doi = "10.1016/S1388-2481(02)00517-9",

language = "English",

volume = "5",

pages = "6--11",

journal = "Electrochemistry Communications",

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T1 - In situ electrochemical-ATR-FTIR spectroscopic studies on solution phase 2,4,6-tri-substituted phenoxyl radicals

AU - Webster, Richard D.

PY - 2003/1/1

Y1 - 2003/1/1

N2 - 2,4,6-Tri-tert-butylphenolate and 2,6-di-tert-butyl-4- methoxyphenolate (prepared by reacting the corresponding phenols with dry Et4NOH) were oxidised by one-electron in CH3CN at room temperature (with 0.2 M Bu4NPF6 as the supporting electrolyte) in a controlled potential electrolysis cell at negative potentials (-0.68 to -0.84 V vs. Fc/Fc+ (Fc = ferrocene)) to produce moderately stable phenoxyl radicals. The oxidation reaction was monitored using in situ FTIR spectroscopy between 1800-1000 cm-1 with an attenuated total reflectance (ATR) probe containing a diamond composite sensor inserted into the working electrode compartment of the electrolysis cell. Analysis of the data obtained during the chemically reversible oxidation of the phenolate anions allowed the identification of several IR absorption bands that could be assigned to the phenoxyl radicals with notable bands observed at 1592-1573 cm-1 and 1505-1509 cm-1 that were assigned to the ν8a(CoCm ring stretch) and ν7a(Ca-O. stretch) modes, respectively.

AB - 2,4,6-Tri-tert-butylphenolate and 2,6-di-tert-butyl-4- methoxyphenolate (prepared by reacting the corresponding phenols with dry Et4NOH) were oxidised by one-electron in CH3CN at room temperature (with 0.2 M Bu4NPF6 as the supporting electrolyte) in a controlled potential electrolysis cell at negative potentials (-0.68 to -0.84 V vs. Fc/Fc+ (Fc = ferrocene)) to produce moderately stable phenoxyl radicals. The oxidation reaction was monitored using in situ FTIR spectroscopy between 1800-1000 cm-1 with an attenuated total reflectance (ATR) probe containing a diamond composite sensor inserted into the working electrode compartment of the electrolysis cell. Analysis of the data obtained during the chemically reversible oxidation of the phenolate anions allowed the identification of several IR absorption bands that could be assigned to the phenoxyl radicals with notable bands observed at 1592-1573 cm-1 and 1505-1509 cm-1 that were assigned to the ν8a(CoCm ring stretch) and ν7a(Ca-O. stretch) modes, respectively.

KW - Attenuated total reflectance

KW - FTIR spectroscopy

KW - Phenol

KW - Phenolate anion

KW - Phenoxyl radical

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U2 - 10.1016/S1388-2481(02)00517-9

DO - 10.1016/S1388-2481(02)00517-9

M3 - Article

SN - 1388-2481

VL - 5

SP - 6

EP - 11

JO - Electrochemistry Communications

JF - Electrochemistry Communications

IS - 1

ER -

In situ electrochemical-ATR-FTIR spectroscopic studies on solution phase 2,4,6-tri-substituted phenoxyl radicals

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