The Methyl(cyclam)nickel(III) Dication in Aqueous Solutions: Determination of the Equilibrium Constant of Homolysis, Kinetics of O2 Insertion, and Methyl Transfer to Cr2+ aq

Alexandra Sauer; Haim Cohen; Dan Meyerstein

doi:10.1021/ic00298a015

The Methyl(cyclam)nickel(III) Dication in Aqueous Solutions: Determination of the Equilibrium Constant of Homolysis, Kinetics of O₂ Insertion, and Methyl Transfer to Cr²⁺ _aq

Alexandra Sauer
, Haim Cohen
, Dan Meyerstein

Ben-Gurion University of the Negev

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

71 Scopus citations

Abstract

The reaction of methyl radicals with LNi²⁺, L = cyclam, proceeds via LNi²⁺ + ^.CH₃ ⇋ L(H₂O)Ni^III-CH₃²⁺, K = 1.1 × 10⁷ M^-1, ^.CH₃ + L(H₂O)Ni^III-CH₃²⁺ → LNi²⁺ + C₂H₆. In the presence of dioxygen L(H₂O)Ni^III-CH₃²⁺ decomposes via homolysis followed by O₂ + ^.CH₃ → ^.O₂CH₃ and ^.O₂CH₃ + LNi²⁺ → L(H₂O)Ni^III-O₂CH₃²⁺. L(H₂O)Ni^III-CH₃²⁺ reacts with Cr(H₂O)₆²⁺ via L(H₂O)Ni^III-CH₃²⁺ + Cr(H₂O)₆²⁺ → LNi²⁺ + (H₂O)₅Cr^III-CH₃²⁺. The kinetics of these reactions and the properties of the new intermediates are discussed, and their relevance as models for biological systems is pointed out.

Original language	English
Pages (from-to)	4578-4581
Number of pages	4
Journal	Inorganic Chemistry
Volume	27
Issue number	25
DOIs	https://doi.org/10.1021/ic00298a015
State	Published - 1 Dec 1988
Externally published	Yes

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@article{5c9dd95013904b8ca34ad4cc95b1c51a,

title = "The Methyl(cyclam)nickel(III) Dication in Aqueous Solutions: Determination of the Equilibrium Constant of Homolysis, Kinetics of O2 Insertion, and Methyl Transfer to Cr2+ aq",

abstract = "The reaction of methyl radicals with LNi2+, L = cyclam, proceeds via LNi2+ + .CH3 ⇋ L(H2O)NiIII-CH32+, K = 1.1 × 107 M-1, .CH3 + L(H2O)NiIII-CH32+ → LNi2+ + C2H6. In the presence of dioxygen L(H2O)NiIII-CH32+ decomposes via homolysis followed by O2 + .CH3 → .O2CH3 and .O2CH3 + LNi2+ → L(H2O)NiIII-O2CH32+. L(H2O)NiIII-CH32+ reacts with Cr(H2O)62+ via L(H2O)NiIII-CH32+ + Cr(H2O)62+ → LNi2+ + (H2O)5CrIII-CH32+. The kinetics of these reactions and the properties of the new intermediates are discussed, and their relevance as models for biological systems is pointed out.",

author = "Alexandra Sauer and Haim Cohen and Dan Meyerstein",

year = "1988",

month = dec,

day = "1",

doi = "10.1021/ic00298a015",

language = "אנגלית",

volume = "27",

pages = "4578--4581",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "25",

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T1 - The Methyl(cyclam)nickel(III) Dication in Aqueous Solutions

T2 - Determination of the Equilibrium Constant of Homolysis, Kinetics of O2 Insertion, and Methyl Transfer to Cr2+ aq

AU - Sauer, Alexandra

AU - Cohen, Haim

AU - Meyerstein, Dan

PY - 1988/12/1

Y1 - 1988/12/1

N2 - The reaction of methyl radicals with LNi2+, L = cyclam, proceeds via LNi2+ + .CH3 ⇋ L(H2O)NiIII-CH32+, K = 1.1 × 107 M-1, .CH3 + L(H2O)NiIII-CH32+ → LNi2+ + C2H6. In the presence of dioxygen L(H2O)NiIII-CH32+ decomposes via homolysis followed by O2 + .CH3 → .O2CH3 and .O2CH3 + LNi2+ → L(H2O)NiIII-O2CH32+. L(H2O)NiIII-CH32+ reacts with Cr(H2O)62+ via L(H2O)NiIII-CH32+ + Cr(H2O)62+ → LNi2+ + (H2O)5CrIII-CH32+. The kinetics of these reactions and the properties of the new intermediates are discussed, and their relevance as models for biological systems is pointed out.

AB - The reaction of methyl radicals with LNi2+, L = cyclam, proceeds via LNi2+ + .CH3 ⇋ L(H2O)NiIII-CH32+, K = 1.1 × 107 M-1, .CH3 + L(H2O)NiIII-CH32+ → LNi2+ + C2H6. In the presence of dioxygen L(H2O)NiIII-CH32+ decomposes via homolysis followed by O2 + .CH3 → .O2CH3 and .O2CH3 + LNi2+ → L(H2O)NiIII-O2CH32+. L(H2O)NiIII-CH32+ reacts with Cr(H2O)62+ via L(H2O)NiIII-CH32+ + Cr(H2O)62+ → LNi2+ + (H2O)5CrIII-CH32+. The kinetics of these reactions and the properties of the new intermediates are discussed, and their relevance as models for biological systems is pointed out.

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DO - 10.1021/ic00298a015

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SN - 0020-1669

VL - 27

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EP - 4581

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 25

ER -

The Methyl(cyclam)nickel(III) Dication in Aqueous Solutions: Determination of the Equilibrium Constant of Homolysis, Kinetics of O₂ Insertion, and Methyl Transfer to Cr²⁺ _aq

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