Oxidation of copper(II) bis(glycinate) by methyl free radicals in aqueous solutions. A pulse-radiolysis study

Mohamad Masarwa; Robert Glaser; Haim Cohen; Dan Meyerstein

doi:10.1021/ic00350a006

Oxidation of copper(II) bis(glycinate) by methyl free radicals in aqueous solutions. A pulse-radiolysis study

Mohamad Masarwa, Robert Glaser, Haim Cohen, Dan Meyerstein

Department of Chemistry

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

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Abstract

The reaction of -CH3 free radicals with Cun(NH₂CH₂CO₂)₂ in aqueous solutions was studied. The formation of the unstable intermediate (NH₂CH₂CO₂)₂Culn-CH₃(aq) in this reaction was observed. This intermediate decomposes into Cu111-(NH₂CH₂CO₂)²⁺(aq) + CH₄. The formation of Cum(NH₂CH₂COf)²⁺(aq) is not observed, as this complex is short-lived under these conditions and decomposes via ligand oxidation. The *CH₃ free radicals react with the transient complex (NH₂CH₂CO₂)₂Cum-CH₃(aq) to form ethane and CuM(NH₂CH₂COf)₂; the specific rate of this reaction approaches the diffusion-controlled limit. The results thus point out that aliphatic free radicals can oxidize copper(Il) complexes to copper(HI) complexes. The results suggest that the reactions of aliphatic free radicals with copper complexes might cause the reported radiosensitization by copper compounds.

Original language	English
Pages (from-to)	5031-5035
Number of pages	5
Journal	Inorganic Chemistry
Volume	29
Issue number	25
DOIs	https://doi.org/10.1021/ic00350a006
State	Published - 1 Jan 1990

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{ec82014bb82a4ba79242e649fb858889,

title = "Oxidation of copper(II) bis(glycinate) by methyl free radicals in aqueous solutions. A pulse-radiolysis study",

abstract = "The reaction of -CH3 free radicals with Cun(NH2CH2CO2)2 in aqueous solutions was studied. The formation of the unstable intermediate (NH2CH2CO2)2Culn-CH3(aq) in this reaction was observed. This intermediate decomposes into Cu111-(NH2CH2CO2)2+(aq) + CH4. The formation of Cum(NH2CH2COf)2+(aq) is not observed, as this complex is short-lived under these conditions and decomposes via ligand oxidation. The *CH3 free radicals react with the transient complex (NH2CH2CO2)2Cum-CH3(aq) to form ethane and CuM(NH2CH2COf)2; the specific rate of this reaction approaches the diffusion-controlled limit. The results thus point out that aliphatic free radicals can oxidize copper(Il) complexes to copper(HI) complexes. The results suggest that the reactions of aliphatic free radicals with copper complexes might cause the reported radiosensitization by copper compounds.",

author = "Mohamad Masarwa and Robert Glaser and Haim Cohen and Dan Meyerstein",

year = "1990",

month = jan,

day = "1",

doi = "10.1021/ic00350a006",

language = "English",

volume = "29",

pages = "5031--5035",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

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T1 - Oxidation of copper(II) bis(glycinate) by methyl free radicals in aqueous solutions. A pulse-radiolysis study

AU - Masarwa, Mohamad

AU - Glaser, Robert

AU - Cohen, Haim

AU - Meyerstein, Dan

PY - 1990/1/1

Y1 - 1990/1/1

N2 - The reaction of -CH3 free radicals with Cun(NH2CH2CO2)2 in aqueous solutions was studied. The formation of the unstable intermediate (NH2CH2CO2)2Culn-CH3(aq) in this reaction was observed. This intermediate decomposes into Cu111-(NH2CH2CO2)2+(aq) + CH4. The formation of Cum(NH2CH2COf)2+(aq) is not observed, as this complex is short-lived under these conditions and decomposes via ligand oxidation. The *CH3 free radicals react with the transient complex (NH2CH2CO2)2Cum-CH3(aq) to form ethane and CuM(NH2CH2COf)2; the specific rate of this reaction approaches the diffusion-controlled limit. The results thus point out that aliphatic free radicals can oxidize copper(Il) complexes to copper(HI) complexes. The results suggest that the reactions of aliphatic free radicals with copper complexes might cause the reported radiosensitization by copper compounds.

AB - The reaction of -CH3 free radicals with Cun(NH2CH2CO2)2 in aqueous solutions was studied. The formation of the unstable intermediate (NH2CH2CO2)2Culn-CH3(aq) in this reaction was observed. This intermediate decomposes into Cu111-(NH2CH2CO2)2+(aq) + CH4. The formation of Cum(NH2CH2COf)2+(aq) is not observed, as this complex is short-lived under these conditions and decomposes via ligand oxidation. The *CH3 free radicals react with the transient complex (NH2CH2CO2)2Cum-CH3(aq) to form ethane and CuM(NH2CH2COf)2; the specific rate of this reaction approaches the diffusion-controlled limit. The results thus point out that aliphatic free radicals can oxidize copper(Il) complexes to copper(HI) complexes. The results suggest that the reactions of aliphatic free radicals with copper complexes might cause the reported radiosensitization by copper compounds.

UR - http://www.scopus.com/inward/record.url?scp=0011496861&partnerID=8YFLogxK

U2 - 10.1021/ic00350a006

DO - 10.1021/ic00350a006

M3 - Article

AN - SCOPUS:0011496861

SN - 0020-1669

VL - 29

SP - 5031

EP - 5035

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 25

ER -

Oxidation of copper(II) bis(glycinate) by methyl free radicals in aqueous solutions. A pulse-radiolysis study

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