Metal Induced Decarboxylation of Aliphatic Free Radicals. I. Kinetics of the Reactions of Copper(I) and Copper(II) Ions with the 2‐Methyl‐2‐Carboxylicacid‐Propyl Free Radical in Aqueous Solutions. A Pulse Radiolysis Study

Mohamed Masarwa; Haim Cohen; Jacob Saar; Dan Meyerstein

doi:10.1002/ijch.199000038

Metal Induced Decarboxylation of Aliphatic Free Radicals. I. Kinetics of the Reactions of Copper(I) and Copper(II) Ions with the 2‐Methyl‐2‐Carboxylicacid‐Propyl Free Radical in Aqueous Solutions. A Pulse Radiolysis Study

Mohamed Masarwa, Haim Cohen, Jacob Saar, Dan Meyerstein

Department of Chemistry

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Abstract

CH₂C(CH₃)₂CO₂H free radicals react with Cu²⁺_aq to form Cu^III‐CH₂C(CH₃)₂CO₂H²⁺_aq, which probably is rapidly transformed into intermediate I. This intermediate decomposes into Cu⁺_aq + CO₂ + CH₂=C(CH₃)₂. This is the first system in which a metal ion induced β‐carboxyl elimination reaction was observed. ·CH₂C(CH₃)₂CO₂H free radicals react with Cu^III‐CH₂C(CH₃)₂CO₂H²⁺_aq to form Cu²⁺_aq and a mixture of (‐CH₂C(CH₃)₂CO₂H)₂, (CH₃)₃CCO₂H, and HOCH₂C(CH₃)₂CO₂H. CH₂C(CH₃)₂CO₂H reacts with Cu⁺_aq to form Cu^II‐CH₂C(CH₃)₂CO₂H⁺_aq. The latter intermediate decomposes both via homolysis and by a reaction with Cu²⁺_aq to form 2Cu²⁺_aq + (CH₃)₃CCO₂H. The spectra of the intermediates and the kinetics of reaction are reported.

Original language	English
Pages (from-to)	361-368
Number of pages	8
Journal	Israel Journal of Chemistry
Volume	30
Issue number	4
DOIs	https://doi.org/10.1002/ijch.199000038
State	Published - 1 Jan 1990

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Masarwa, M., Cohen, H., Saar, J., & Meyerstein, D. (1990). Metal Induced Decarboxylation of Aliphatic Free Radicals. I. Kinetics of the Reactions of Copper(I) and Copper(II) Ions with the 2‐Methyl‐2‐Carboxylicacid‐Propyl Free Radical in Aqueous Solutions. A Pulse Radiolysis Study. Israel Journal of Chemistry, 30(4), 361-368. https://doi.org/10.1002/ijch.199000038

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title = "Metal Induced Decarboxylation of Aliphatic Free Radicals. I. Kinetics of the Reactions of Copper(I) and Copper(II) Ions with the 2‐Methyl‐2‐Carboxylicacid‐Propyl Free Radical in Aqueous Solutions. A Pulse Radiolysis Study",

abstract = "CH2C(CH3)2CO2H free radicals react with Cu2+aq to form CuIII‐CH2C(CH3)2CO2H2+aq, which probably is rapidly transformed into intermediate I. This intermediate decomposes into Cu+aq + CO2 + CH2=C(CH3)2. This is the first system in which a metal ion induced β‐carboxyl elimination reaction was observed. ·CH2C(CH3)2CO2H free radicals react with CuIII‐CH2C(CH3)2CO2H2+aq to form Cu2+aq and a mixture of (‐CH2C(CH3)2CO2H)2, (CH3)3CCO2H, and HOCH2C(CH3)2CO2H. CH2C(CH3)2CO2H reacts with Cu+aq to form CuII‐CH2C(CH3)2CO2H+aq. The latter intermediate decomposes both via homolysis and by a reaction with Cu2+aq to form 2Cu2+aq + (CH3)3CCO2H. The spectra of the intermediates and the kinetics of reaction are reported.",

author = "Mohamed Masarwa and Haim Cohen and Jacob Saar and Dan Meyerstein",

year = "1990",

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doi = "10.1002/ijch.199000038",

language = "English",

volume = "30",

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journal = "Israel Journal of Chemistry",

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Masarwa, M, Cohen, H, Saar, J & Meyerstein, D 1990, 'Metal Induced Decarboxylation of Aliphatic Free Radicals. I. Kinetics of the Reactions of Copper(I) and Copper(II) Ions with the 2‐Methyl‐2‐Carboxylicacid‐Propyl Free Radical in Aqueous Solutions. A Pulse Radiolysis Study', Israel Journal of Chemistry, vol. 30, no. 4, pp. 361-368. https://doi.org/10.1002/ijch.199000038

Metal Induced Decarboxylation of Aliphatic Free Radicals. I. Kinetics of the Reactions of Copper(I) and Copper(II) Ions with the 2‐Methyl‐2‐Carboxylicacid‐Propyl Free Radical in Aqueous Solutions. A Pulse Radiolysis Study. / Masarwa, Mohamed; Cohen, Haim; Saar, Jacob et al.
In: Israel Journal of Chemistry, Vol. 30, No. 4, 01.01.1990, p. 361-368.

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

TY - JOUR

T1 - Metal Induced Decarboxylation of Aliphatic Free Radicals. I. Kinetics of the Reactions of Copper(I) and Copper(II) Ions with the 2‐Methyl‐2‐Carboxylicacid‐Propyl Free Radical in Aqueous Solutions. A Pulse Radiolysis Study

AU - Masarwa, Mohamed

AU - Cohen, Haim

AU - Saar, Jacob

AU - Meyerstein, Dan

PY - 1990/1/1

Y1 - 1990/1/1

N2 - CH2C(CH3)2CO2H free radicals react with Cu2+aq to form CuIII‐CH2C(CH3)2CO2H2+aq, which probably is rapidly transformed into intermediate I. This intermediate decomposes into Cu+aq + CO2 + CH2=C(CH3)2. This is the first system in which a metal ion induced β‐carboxyl elimination reaction was observed. ·CH2C(CH3)2CO2H free radicals react with CuIII‐CH2C(CH3)2CO2H2+aq to form Cu2+aq and a mixture of (‐CH2C(CH3)2CO2H)2, (CH3)3CCO2H, and HOCH2C(CH3)2CO2H. CH2C(CH3)2CO2H reacts with Cu+aq to form CuII‐CH2C(CH3)2CO2H+aq. The latter intermediate decomposes both via homolysis and by a reaction with Cu2+aq to form 2Cu2+aq + (CH3)3CCO2H. The spectra of the intermediates and the kinetics of reaction are reported.

AB - CH2C(CH3)2CO2H free radicals react with Cu2+aq to form CuIII‐CH2C(CH3)2CO2H2+aq, which probably is rapidly transformed into intermediate I. This intermediate decomposes into Cu+aq + CO2 + CH2=C(CH3)2. This is the first system in which a metal ion induced β‐carboxyl elimination reaction was observed. ·CH2C(CH3)2CO2H free radicals react with CuIII‐CH2C(CH3)2CO2H2+aq to form Cu2+aq and a mixture of (‐CH2C(CH3)2CO2H)2, (CH3)3CCO2H, and HOCH2C(CH3)2CO2H. CH2C(CH3)2CO2H reacts with Cu+aq to form CuII‐CH2C(CH3)2CO2H+aq. The latter intermediate decomposes both via homolysis and by a reaction with Cu2+aq to form 2Cu2+aq + (CH3)3CCO2H. The spectra of the intermediates and the kinetics of reaction are reported.

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U2 - 10.1002/ijch.199000038

DO - 10.1002/ijch.199000038

M3 - Article

AN - SCOPUS:85005675357

SN - 0021-2148

VL - 30

SP - 361

EP - 368

JO - Israel Journal of Chemistry

JF - Israel Journal of Chemistry

IS - 4

ER -

Metal Induced Decarboxylation of Aliphatic Free Radicals. I. Kinetics of the Reactions of Copper(I) and Copper(II) Ions with the 2‐Methyl‐2‐Carboxylicacid‐Propyl Free Radical in Aqueous Solutions. A Pulse Radiolysis Study

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