Reaction of an electron-rich radical-cation with electrogenerated radicals in indirect anodic oxidation

M. Michman; M. Oron

doi:10.1016/0013-4686(94)00226-6

Reaction of an electron-rich radical-cation with electrogenerated radicals in indirect anodic oxidation

M. Michman^*, M. Oron

^*Corresponding author for this work

Institute of Chemistry

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

8 Scopus citations

Abstract

1,4-Di-tert-butyl-2,5-dimethoxybenzene (A) reversibly forms a radical-cation (B) at E^a_{1 2} = 1.15 V (Pt, vs. Ag⁺ | AgCl | (sat.) KCl, 18°C) in dry and in aqueous acetonitrile. B is stable in many solvents, is unreactive towards nucleophiles but reacts readily with radicals. This special activity pattern appears to be characteristic of electron rich radical-cations and is utilized to investigate the linkage of catalysed electro-oxidation of water to organic electrooxidations. When electrolysis of A is conducted in presence of both water and either RuCl₃ · 3H₂O or Ru(acac)₃ it reacts to yield 2,5-di-tert-butyl-1,4-benzoquinone (D), with practically 100% selectivity. RuCl₃ · 3H₂O and Ru(acac)₃ are catalysts for the electrooxidation of water and the role of electrogenerated radicals in the process is indicated, in support of previous work. RuCl₃ · 3H₂O also catalyzes the homogeneous oxidation of A to D by H₂O₂ in a semblance to the Fenton reaction.

Original language	English
Pages (from-to)	2781-2787
Number of pages	7
Journal	Electrochimica Acta
Volume	39
Issue number	18
DOIs	https://doi.org/10.1016/0013-4686(94)00226-6
State	Published - Dec 1994

Keywords

1
2
4-benzoquinone.
4-di-tert-butyl-2
5-di-tert-butyl-1
5-dimethoxybenzene
catalysis
electro-oxidation
ruthenium tris-acetylacetonate

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10.1016/0013-4686(94)00226-6

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title = "Reaction of an electron-rich radical-cation with electrogenerated radicals in indirect anodic oxidation",

abstract = "1,4-Di-tert-butyl-2,5-dimethoxybenzene (A) reversibly forms a radical-cation (B) at Ea 1 2 = 1.15 V (Pt, vs. Ag+ | AgCl | (sat.) KCl, 18°C) in dry and in aqueous acetonitrile. B is stable in many solvents, is unreactive towards nucleophiles but reacts readily with radicals. This special activity pattern appears to be characteristic of electron rich radical-cations and is utilized to investigate the linkage of catalysed electro-oxidation of water to organic electrooxidations. When electrolysis of A is conducted in presence of both water and either RuCl3 · 3H2O or Ru(acac)3 it reacts to yield 2,5-di-tert-butyl-1,4-benzoquinone (D), with practically 100% selectivity. RuCl3 · 3H2O and Ru(acac)3 are catalysts for the electrooxidation of water and the role of electrogenerated radicals in the process is indicated, in support of previous work. RuCl3 · 3H2O also catalyzes the homogeneous oxidation of A to D by H2O2 in a semblance to the Fenton reaction.",

keywords = "1, 2, 4-benzoquinone., 4-di-tert-butyl-2, 5-di-tert-butyl-1, 5-dimethoxybenzene, catalysis, electro-oxidation, ruthenium tris-acetylacetonate",

author = "M. Michman and M. Oron",

year = "1994",

month = dec,

doi = "10.1016/0013-4686(94)00226-6",

language = "אנגלית",

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journal = "Electrochimica Acta",

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T1 - Reaction of an electron-rich radical-cation with electrogenerated radicals in indirect anodic oxidation

AU - Michman, M.

AU - Oron, M.

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N2 - 1,4-Di-tert-butyl-2,5-dimethoxybenzene (A) reversibly forms a radical-cation (B) at Ea 1 2 = 1.15 V (Pt, vs. Ag+ | AgCl | (sat.) KCl, 18°C) in dry and in aqueous acetonitrile. B is stable in many solvents, is unreactive towards nucleophiles but reacts readily with radicals. This special activity pattern appears to be characteristic of electron rich radical-cations and is utilized to investigate the linkage of catalysed electro-oxidation of water to organic electrooxidations. When electrolysis of A is conducted in presence of both water and either RuCl3 · 3H2O or Ru(acac)3 it reacts to yield 2,5-di-tert-butyl-1,4-benzoquinone (D), with practically 100% selectivity. RuCl3 · 3H2O and Ru(acac)3 are catalysts for the electrooxidation of water and the role of electrogenerated radicals in the process is indicated, in support of previous work. RuCl3 · 3H2O also catalyzes the homogeneous oxidation of A to D by H2O2 in a semblance to the Fenton reaction.

AB - 1,4-Di-tert-butyl-2,5-dimethoxybenzene (A) reversibly forms a radical-cation (B) at Ea 1 2 = 1.15 V (Pt, vs. Ag+ | AgCl | (sat.) KCl, 18°C) in dry and in aqueous acetonitrile. B is stable in many solvents, is unreactive towards nucleophiles but reacts readily with radicals. This special activity pattern appears to be characteristic of electron rich radical-cations and is utilized to investigate the linkage of catalysed electro-oxidation of water to organic electrooxidations. When electrolysis of A is conducted in presence of both water and either RuCl3 · 3H2O or Ru(acac)3 it reacts to yield 2,5-di-tert-butyl-1,4-benzoquinone (D), with practically 100% selectivity. RuCl3 · 3H2O and Ru(acac)3 are catalysts for the electrooxidation of water and the role of electrogenerated radicals in the process is indicated, in support of previous work. RuCl3 · 3H2O also catalyzes the homogeneous oxidation of A to D by H2O2 in a semblance to the Fenton reaction.

KW - 1

KW - 2

KW - 4-benzoquinone.

KW - 4-di-tert-butyl-2

KW - 5-di-tert-butyl-1

KW - 5-dimethoxybenzene

KW - catalysis

KW - electro-oxidation

KW - ruthenium tris-acetylacetonate

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AN - SCOPUS:0001309164

SN - 0013-4686

VL - 39

SP - 2781

EP - 2787

JO - Electrochimica Acta

JF - Electrochimica Acta

IS - 18

ER -

Reaction of an electron-rich radical-cation with electrogenerated radicals in indirect anodic oxidation

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