Complexation of a Nickel(III) Macrocyclic Complex by Sulfate Ion. A Pulse Radiolytic Study

Haim Cohen; Dan Meyerstein; Louis J. Kirschenbaum; Esther Zeigerson; Moshe Jaacobi; Efrat Fuchs; Gregory Ginzburg; Louis J. Kirschenbaum

doi:10.1021/ic50200a026

Complexation of a Nickel(III) Macrocyclic Complex by Sulfate Ion. A Pulse Radiolytic Study

Haim Cohen
, Dan Meyerstein
, Louis J. Kirschenbaum
, Esther Zeigerson
, Moshe Jaacobi
, Efrat Fuchs
, Gregory Ginzburg
, Louis J. Kirschenbaum

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

47 Scopus citations

Abstract

The kinetics of oxidation of Ni₁₁[meso-Me₆[14]aneN₄] (NiL²⁺) to Ni(III) by OH radical and subsequent complexation by sulfate ion have been studied in acidic aqueous media at 22°C and μ=0.01-0.3 M by the pulse radiolytic technique. Results indicate that NiL3+hydrolyzes with a pK+3.7±0.2 but that, at least up to pH 5.2, substitution by SO₄ ^{^2-} occurs only on the unhydrolyzed species with a rate constant of 1X10₆ M^-1 s^-1 at μ=0.03 M. The equilibrium constant for sulfate complexation is 3.0X10₄ M^-1 at μ=0.03 M and the product of the reaction is identical with the stable NiLSO₄+species produced by the electrochemical oxidation of NiL2+in sulfate media. The results demonstrate the stabilization of NiIII by sulfate complexation.

Original language	English
Pages (from-to)	2763-2766
Number of pages	4
Journal	Inorganic Chemistry
Volume	18
Issue number	10
DOIs	https://doi.org/10.1021/ic50200a026
State	Published - 1979
Externally published	Yes

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@article{6364c16a088b4f1c8c2026da9ef41242,

title = "Complexation of a Nickel(III) Macrocyclic Complex by Sulfate Ion. A Pulse Radiolytic Study",

abstract = "The kinetics of oxidation of Ni11[meso-Me6[14]aneN4] (NiL2+) to Ni(III) by OH radical and subsequent complexation by sulfate ion have been studied in acidic aqueous media at 22°C and μ=0.01-0.3 M by the pulse radiolytic technique. Results indicate that NiL3+hydrolyzes with a pK+3.7±0.2 but that, at least up to pH 5.2, substitution by SO4 2- occurs only on the unhydrolyzed species with a rate constant of 1X106 M-1 s-1 at μ=0.03 M. The equilibrium constant for sulfate complexation is 3.0X104 M-1 at μ=0.03 M and the product of the reaction is identical with the stable NiLSO4+species produced by the electrochemical oxidation of NiL2+in sulfate media. The results demonstrate the stabilization of NiIII by sulfate complexation.",

author = "Haim Cohen and Dan Meyerstein and Kirschenbaum, \{Louis J.\} and Esther Zeigerson and Moshe Jaacobi and Efrat Fuchs and Gregory Ginzburg and Kirschenbaum, \{Louis J.\}",

year = "1979",

doi = "10.1021/ic50200a026",

language = "אנגלית",

volume = "18",

pages = "2763--2766",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "10",

}

TY - JOUR

T1 - Complexation of a Nickel(III) Macrocyclic Complex by Sulfate Ion. A Pulse Radiolytic Study

AU - Cohen, Haim

AU - Meyerstein, Dan

AU - Kirschenbaum, Louis J.

AU - Zeigerson, Esther

AU - Jaacobi, Moshe

AU - Fuchs, Efrat

AU - Ginzburg, Gregory

AU - Kirschenbaum, Louis J.

PY - 1979

Y1 - 1979

N2 - The kinetics of oxidation of Ni11[meso-Me6[14]aneN4] (NiL2+) to Ni(III) by OH radical and subsequent complexation by sulfate ion have been studied in acidic aqueous media at 22°C and μ=0.01-0.3 M by the pulse radiolytic technique. Results indicate that NiL3+hydrolyzes with a pK+3.7±0.2 but that, at least up to pH 5.2, substitution by SO4 2- occurs only on the unhydrolyzed species with a rate constant of 1X106 M-1 s-1 at μ=0.03 M. The equilibrium constant for sulfate complexation is 3.0X104 M-1 at μ=0.03 M and the product of the reaction is identical with the stable NiLSO4+species produced by the electrochemical oxidation of NiL2+in sulfate media. The results demonstrate the stabilization of NiIII by sulfate complexation.

AB - The kinetics of oxidation of Ni11[meso-Me6[14]aneN4] (NiL2+) to Ni(III) by OH radical and subsequent complexation by sulfate ion have been studied in acidic aqueous media at 22°C and μ=0.01-0.3 M by the pulse radiolytic technique. Results indicate that NiL3+hydrolyzes with a pK+3.7±0.2 but that, at least up to pH 5.2, substitution by SO4 2- occurs only on the unhydrolyzed species with a rate constant of 1X106 M-1 s-1 at μ=0.03 M. The equilibrium constant for sulfate complexation is 3.0X104 M-1 at μ=0.03 M and the product of the reaction is identical with the stable NiLSO4+species produced by the electrochemical oxidation of NiL2+in sulfate media. The results demonstrate the stabilization of NiIII by sulfate complexation.

UR - https://www.scopus.com/pages/publications/0013385131

U2 - 10.1021/ic50200a026

DO - 10.1021/ic50200a026

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AN - SCOPUS:0013385131

SN - 0020-1669

VL - 18

SP - 2763

EP - 2766

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 10

ER -

Complexation of a Nickel(III) Macrocyclic Complex by Sulfate Ion. A Pulse Radiolytic Study

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