Formation and Decomposition of Transient Complexes with a Copper-Carbon-Bond in the Reaction of Copper(I)Phenanthroline with Aliphatic Free Radicals. A Pulse Radiolysis Study

Sara Goldstein; Gidon Czapski; Haim Cohen; Dan Meyerstein

doi:10.1021/ic00296a011

Formation and Decomposition of Transient Complexes with a Copper-Carbon-Bond in the Reaction of Copper(I)Phenanthroline with Aliphatic Free Radicals. A Pulse Radiolysis Study

Sara Goldstein, Gidon Czapski, Haim Cohen, Dan Meyerstein

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

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Abstract

The oxidation of copper(I) phenanthroline by ^•CH₂CH₂OH and ^•CH₂C(CH₃)₂OH free radicals yields ethylene and 2-methylpropene, respectively. During this process transients with a copper-carbon σ-bond have been observed with an absorbance similar to that of copper(I) phenanthroline in the visible region. Rate constants for the formation of these transients are estimated to be larger than 10¹⁰M^-1s^-1. These intermediates decompose via a β-hydroxyl elimination reaction with specific rate constants of (1.7 ± 0.4) X 10³and (1.1 ± 0.3) X 10⁴s^-1for ^•CH₂C(CH₃)₂OH and ^•CH₂CH₂OH in the pH range 4-10, respectively. The mechanism of the decomposition is discussed, and a stability constant for the ligation of ^•CH₂C(CH₃)₂OH and ^•CH₂CH₂OH to the cuprous complex is estimated to be larger than 6 X 10⁶M^-1.

Original language	English
Pages (from-to)	4130-4135
Number of pages	6
Journal	Inorganic Chemistry
Volume	27
Issue number	23
DOIs	https://doi.org/10.1021/ic00296a011
State	Published - 1 Nov 1988
Externally published	Yes

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title = "Formation and Decomposition of Transient Complexes with a Copper-Carbon-Bond in the Reaction of Copper(I)Phenanthroline with Aliphatic Free Radicals. A Pulse Radiolysis Study",

abstract = "The oxidation of copper(I) phenanthroline by •CH2CH2OH and •CH2C(CH3)2OH free radicals yields ethylene and 2-methylpropene, respectively. During this process transients with a copper-carbon σ-bond have been observed with an absorbance similar to that of copper(I) phenanthroline in the visible region. Rate constants for the formation of these transients are estimated to be larger than 1010M-1s-1. These intermediates decompose via a β-hydroxyl elimination reaction with specific rate constants of (1.7 ± 0.4) X 103and (1.1 ± 0.3) X 104s-1for •CH2C(CH3)2OH and •CH2CH2OH in the pH range 4-10, respectively. The mechanism of the decomposition is discussed, and a stability constant for the ligation of •CH2C(CH3)2OH and •CH2CH2OH to the cuprous complex is estimated to be larger than 6 X 106M-1.",

author = "Sara Goldstein and Gidon Czapski and Haim Cohen and Dan Meyerstein",

year = "1988",

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doi = "10.1021/ic00296a011",

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AU - Goldstein, Sara

AU - Czapski, Gidon

AU - Cohen, Haim

AU - Meyerstein, Dan

PY - 1988/11/1

Y1 - 1988/11/1

N2 - The oxidation of copper(I) phenanthroline by •CH2CH2OH and •CH2C(CH3)2OH free radicals yields ethylene and 2-methylpropene, respectively. During this process transients with a copper-carbon σ-bond have been observed with an absorbance similar to that of copper(I) phenanthroline in the visible region. Rate constants for the formation of these transients are estimated to be larger than 1010M-1s-1. These intermediates decompose via a β-hydroxyl elimination reaction with specific rate constants of (1.7 ± 0.4) X 103and (1.1 ± 0.3) X 104s-1for •CH2C(CH3)2OH and •CH2CH2OH in the pH range 4-10, respectively. The mechanism of the decomposition is discussed, and a stability constant for the ligation of •CH2C(CH3)2OH and •CH2CH2OH to the cuprous complex is estimated to be larger than 6 X 106M-1.

AB - The oxidation of copper(I) phenanthroline by •CH2CH2OH and •CH2C(CH3)2OH free radicals yields ethylene and 2-methylpropene, respectively. During this process transients with a copper-carbon σ-bond have been observed with an absorbance similar to that of copper(I) phenanthroline in the visible region. Rate constants for the formation of these transients are estimated to be larger than 1010M-1s-1. These intermediates decompose via a β-hydroxyl elimination reaction with specific rate constants of (1.7 ± 0.4) X 103and (1.1 ± 0.3) X 104s-1for •CH2C(CH3)2OH and •CH2CH2OH in the pH range 4-10, respectively. The mechanism of the decomposition is discussed, and a stability constant for the ligation of •CH2C(CH3)2OH and •CH2CH2OH to the cuprous complex is estimated to be larger than 6 X 106M-1.

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Formation and Decomposition of Transient Complexes with a Copper-Carbon-Bond in the Reaction of Copper(I)Phenanthroline with Aliphatic Free Radicals. A Pulse Radiolysis Study

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