Oxidation, Reduction, and Copper-Carbon Bond Formation in the Reactions of Copper(II) Tetraglycine with Pulse Radiolytically Generated Free Radicals

Louis J. Kirschenbaua; Dan Meyerstein

doi:10.1021/ic50207a053

Oxidation, Reduction, and Copper-Carbon Bond Formation in the Reactions of Copper(II) Tetraglycine with Pulse Radiolytically Generated Free Radicals

Louis J. Kirschenbaua, Dan Meyerstein

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Abstract

The reactions of copper(II) tetraglycine (Cu^IIG₄) with a variety of aliphatic free radicals and with -Br₂^- and OH have been investigated by the pulse radiolytic technique. Three types of reaction are observed: (i) oxidation of Cu^IIG₄ to Cu^IIIG₄ by Br₂^- and OH; (ii) rapid reduction to copper(I) by CH₂OH, CO₂^-, and (CH₃)₂COH; (iii) formation of unstable copper(III)-carbon-bonded intermediates with lifetimes from several milliseconds to several seconds with CH₂C(CH₃)₂OH, CH₂CO₂^-, and CH₂C(OH)CH₃ radicals. Rate constants are reported for formation and decomposition of all intermediates and the relative instability of neutral Cu^III(H_-2G₄) compared to Cu^III(H_-3G₄) is confirmed by direct observation.

Original language	English
Pages (from-to)	1373-1379
Number of pages	7
Journal	Inorganic Chemistry
Volume	19
Issue number	5
DOIs	https://doi.org/10.1021/ic50207a053
State	Published - 1 Jan 1980
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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title = "Oxidation, Reduction, and Copper-Carbon Bond Formation in the Reactions of Copper(II) Tetraglycine with Pulse Radiolytically Generated Free Radicals",

abstract = "The reactions of copper(II) tetraglycine (CuIIG4) with a variety of aliphatic free radicals and with -Br2- and OH have been investigated by the pulse radiolytic technique. Three types of reaction are observed: (i) oxidation of CuIIG4 to CuIIIG4 by Br2- and OH; (ii) rapid reduction to copper(I) by CH2OH, CO2-, and (CH3)2COH; (iii) formation of unstable copper(III)-carbon-bonded intermediates with lifetimes from several milliseconds to several seconds with CH2C(CH3)2OH, CH2CO2-, and CH2C(OH)CH3 radicals. Rate constants are reported for formation and decomposition of all intermediates and the relative instability of neutral CuIII(H-2G4) compared to CuIII(H-3G4) is confirmed by direct observation.",

author = "Kirschenbaua, {Louis J.} and Dan Meyerstein",

year = "1980",

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doi = "10.1021/ic50207a053",

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T1 - Oxidation, Reduction, and Copper-Carbon Bond Formation in the Reactions of Copper(II) Tetraglycine with Pulse Radiolytically Generated Free Radicals

AU - Kirschenbaua, Louis J.

AU - Meyerstein, Dan

PY - 1980/1/1

Y1 - 1980/1/1

N2 - The reactions of copper(II) tetraglycine (CuIIG4) with a variety of aliphatic free radicals and with -Br2- and OH have been investigated by the pulse radiolytic technique. Three types of reaction are observed: (i) oxidation of CuIIG4 to CuIIIG4 by Br2- and OH; (ii) rapid reduction to copper(I) by CH2OH, CO2-, and (CH3)2COH; (iii) formation of unstable copper(III)-carbon-bonded intermediates with lifetimes from several milliseconds to several seconds with CH2C(CH3)2OH, CH2CO2-, and CH2C(OH)CH3 radicals. Rate constants are reported for formation and decomposition of all intermediates and the relative instability of neutral CuIII(H-2G4) compared to CuIII(H-3G4) is confirmed by direct observation.

AB - The reactions of copper(II) tetraglycine (CuIIG4) with a variety of aliphatic free radicals and with -Br2- and OH have been investigated by the pulse radiolytic technique. Three types of reaction are observed: (i) oxidation of CuIIG4 to CuIIIG4 by Br2- and OH; (ii) rapid reduction to copper(I) by CH2OH, CO2-, and (CH3)2COH; (iii) formation of unstable copper(III)-carbon-bonded intermediates with lifetimes from several milliseconds to several seconds with CH2C(CH3)2OH, CH2CO2-, and CH2C(OH)CH3 radicals. Rate constants are reported for formation and decomposition of all intermediates and the relative instability of neutral CuIII(H-2G4) compared to CuIII(H-3G4) is confirmed by direct observation.

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JO - Inorganic Chemistry

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IS - 5

ER -

Oxidation, Reduction, and Copper-Carbon Bond Formation in the Reactions of Copper(II) Tetraglycine with Pulse Radiolytically Generated Free Radicals

Abstract

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