Effect of Nitrilotriacetate on the Mechanism of Reduction of Copper(II) Ions by a-Hydroxyalkyl Free Radicals via Complexes with Copper-Carbon Bonds as Intermediates. A Pulse-Radiolytic Study

Mohamed Masarwa; Dan Meyerstein; Haim Cohen

doi:10.1021/ic00247a024

Effect of Nitrilotriacetate on the Mechanism of Reduction of Copper(II) Ions by a-Hydroxyalkyl Free Radicals via Complexes with Copper-Carbon Bonds as Intermediates. A Pulse-Radiolytic Study

Mohamed Masarwa
, Dan Meyerstein
, Haim Cohen

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

23 Scopus citations

Abstract

a-Hydroxyalkyl free radicals, ·CR₁R2OH, react with copper(II) nitrilotriacetate, Cu(nta)^-(aq), in aqueous solutions to form the unstable intermediates (nta)Cu^III-CR₁R₂OH-(aq), or (nta)Cu^III-CH_2O^2-(aq). These intermediates decompose by reducing a second Cu^II(nta)^-(aq) complex, i.e. via the reaction (nta)Cu^III-CR₁R₂OH-(aq) + Cu^II(nta)^-(aq) Cu^I(nta)^2-(aq) + Cu^II(nta)-(aq) + CR₁R₂O + H₃0⁺. Unexpectedly, the intermediates do not decompose via first-order processes as expected. The spectrum of (nta)Cu^III-CH₂OH-(aq) is reported. The kinetics of reduction of Co(NH₃)₆³⁺, Ru(NH₃)₆³⁺, and Fe(CN)₆^3-by the latter intermediate are reported.

Original language	English
Pages (from-to)	4897-4900
Number of pages	4
Journal	Inorganic Chemistry
Volume	25
Issue number	27
DOIs	https://doi.org/10.1021/ic00247a024
State	Published - 1 Jan 1986
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{5bda925bfa2b4ac0abcdc614a12077cb,

title = "Effect of Nitrilotriacetate on the Mechanism of Reduction of Copper(II) Ions by a-Hydroxyalkyl Free Radicals via Complexes with Copper-Carbon Bonds as Intermediates. A Pulse-Radiolytic Study",

abstract = "a-Hydroxyalkyl free radicals, ·CR1R2OH, react with copper(II) nitrilotriacetate, Cu(nta)-(aq), in aqueous solutions to form the unstable intermediates (nta)CuIII-CR1R2OH-(aq), or (nta)CuIII-CH2O2-(aq). These intermediates decompose by reducing a second CuII(nta)-(aq) complex, i.e. via the reaction (nta)CuIII-CR1R2OH-(aq) + CuII(nta)-(aq) CuI(nta)2-(aq) + CuII(nta)-(aq) + CR1R2O + H30+. Unexpectedly, the intermediates do not decompose via first-order processes as expected. The spectrum of (nta)CuIII-CH2OH-(aq) is reported. The kinetics of reduction of Co(NH3)63+, Ru(NH3)63+, and Fe(CN)63-by the latter intermediate are reported.",

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

year = "1986",

month = jan,

day = "1",

doi = "10.1021/ic00247a024",

language = "English",

volume = "25",

pages = "4897--4900",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "27",

}

Effect of Nitrilotriacetate on the Mechanism of Reduction of Copper(II) Ions by a-Hydroxyalkyl Free Radicals via Complexes with Copper-Carbon Bonds as Intermediates. A Pulse-Radiolytic Study. / Masarwa, Mohamed; Meyerstein, Dan; Cohen, Haim.
In: Inorganic Chemistry, Vol. 25, No. 27, 01.01.1986, p. 4897-4900.

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

TY - JOUR

T1 - Effect of Nitrilotriacetate on the Mechanism of Reduction of Copper(II) Ions by a-Hydroxyalkyl Free Radicals via Complexes with Copper-Carbon Bonds as Intermediates. A Pulse-Radiolytic Study

AU - Masarwa, Mohamed

AU - Meyerstein, Dan

AU - Cohen, Haim

PY - 1986/1/1

Y1 - 1986/1/1

N2 - a-Hydroxyalkyl free radicals, ·CR1R2OH, react with copper(II) nitrilotriacetate, Cu(nta)-(aq), in aqueous solutions to form the unstable intermediates (nta)CuIII-CR1R2OH-(aq), or (nta)CuIII-CH2O2-(aq). These intermediates decompose by reducing a second CuII(nta)-(aq) complex, i.e. via the reaction (nta)CuIII-CR1R2OH-(aq) + CuII(nta)-(aq) CuI(nta)2-(aq) + CuII(nta)-(aq) + CR1R2O + H30+. Unexpectedly, the intermediates do not decompose via first-order processes as expected. The spectrum of (nta)CuIII-CH2OH-(aq) is reported. The kinetics of reduction of Co(NH3)63+, Ru(NH3)63+, and Fe(CN)63-by the latter intermediate are reported.

AB - a-Hydroxyalkyl free radicals, ·CR1R2OH, react with copper(II) nitrilotriacetate, Cu(nta)-(aq), in aqueous solutions to form the unstable intermediates (nta)CuIII-CR1R2OH-(aq), or (nta)CuIII-CH2O2-(aq). These intermediates decompose by reducing a second CuII(nta)-(aq) complex, i.e. via the reaction (nta)CuIII-CR1R2OH-(aq) + CuII(nta)-(aq) CuI(nta)2-(aq) + CuII(nta)-(aq) + CR1R2O + H30+. Unexpectedly, the intermediates do not decompose via first-order processes as expected. The spectrum of (nta)CuIII-CH2OH-(aq) is reported. The kinetics of reduction of Co(NH3)63+, Ru(NH3)63+, and Fe(CN)63-by the latter intermediate are reported.

UR - https://www.scopus.com/pages/publications/0039576895

U2 - 10.1021/ic00247a024

DO - 10.1021/ic00247a024

M3 - Article

AN - SCOPUS:0039576895

SN - 0020-1669

VL - 25

SP - 4897

EP - 4900

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 27

ER -

Effect of Nitrilotriacetate on the Mechanism of Reduction of Copper(II) Ions by a-Hydroxyalkyl Free Radicals via Complexes with Copper-Carbon Bonds as Intermediates. A Pulse-Radiolytic Study

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