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A Reaction Mechanism for Oxidative Addition of Halogen to Platinum(II), Reductive Elimination of Halide from Platinum(IV) and Halide Assisted Anations of Platinum(IV) Complexes

Elding, Lars Ivar LU and Gustafson, Lena (1976) In Inorganica Chimica Acta 19(2). p.165-171
Abstract (Swedish)
The oxidative addition of iodine to Pt(CN)42− is first-order with respect to iodide, iodine and complex. The reverse reductive elimination of iodide from trans-Pt(CN)4I22- is first-order with respect to iodide and Pt(CN)4I22−. The kinetics for the reaction between bromide and trans-Pt(CN)4ClH2O2− involves a rate-determining reductive elimination of chloride, followed by a rapid oxidative addition of bromine to the formed Pt(CN)42−. The reactions between trans-Pt(CN)4BrH2O− and bromide or chloride can be described as halide assisted anations. The rate constant for the bromide anation is kexp = k′[Br−]2 and for the chloride anation (in the presence of bromide) k′[Br−][Cl−] + k′' [Cl−]2. All reactions were followed using a stopped-flow... (More)
The oxidative addition of iodine to Pt(CN)42− is first-order with respect to iodide, iodine and complex. The reverse reductive elimination of iodide from trans-Pt(CN)4I22- is first-order with respect to iodide and Pt(CN)4I22−. The kinetics for the reaction between bromide and trans-Pt(CN)4ClH2O2− involves a rate-determining reductive elimination of chloride, followed by a rapid oxidative addition of bromine to the formed Pt(CN)42−. The reactions between trans-Pt(CN)4BrH2O− and bromide or chloride can be described as halide assisted anations. The rate constant for the bromide anation is kexp = k′[Br−]2 and for the chloride anation (in the presence of bromide) k′[Br−][Cl−] + k′' [Cl−]2. All reactions were followed using a stopped-flow technique at 25°C in 0.50M perchloric acid medium. The equilibrium constant for the redox equilibrium between Pt(CN)42−, iodine and Pt(CN)4I22− was determined separately to be (1.29 ± 0.03) × 104M−1.
Exploratory stopped-flow experiments indicate that the oxidative addition of chlorine to PtCl42− is first-order with respect to both chlorine and tetrachloroplatinate.
The experimental rate laws can be described by a reaction mechanism which resembles that introduced previously for Pt(II)-catalyzed anations and substitutions, in that both mechanisms can be considered as oxidative additions/reductive eliminations. (Less)
Abstract
The oxidative addition of iodine to Pt(CN)42− is first-order with respect to iodide, iodine and complex. The reverse reductive elimination of iodide from trans-Pt(CN)4I22- is first-order with respect to iodide and Pt(CN)4I22−. The kinetics for the reaction between bromide and trans-Pt(CN)4ClH2O2− involves a rate-determining reductive elimination of chloride, followed by a rapid oxidative addition of bromine to the formed Pt(CN)42−. The reactions between trans-Pt(CN)4BrH2O− and bromide or chloride can be described as halide assisted anations. The rate constant for the bromide anation is kexp = k′[Br−]2 and for the chloride anation (in the presence of bromide) k′[Br−][Cl−] + k′' [Cl−]2. All reactions were followed using a stopped-flow... (More)
The oxidative addition of iodine to Pt(CN)42− is first-order with respect to iodide, iodine and complex. The reverse reductive elimination of iodide from trans-Pt(CN)4I22- is first-order with respect to iodide and Pt(CN)4I22−. The kinetics for the reaction between bromide and trans-Pt(CN)4ClH2O2− involves a rate-determining reductive elimination of chloride, followed by a rapid oxidative addition of bromine to the formed Pt(CN)42−. The reactions between trans-Pt(CN)4BrH2O− and bromide or chloride can be described as halide assisted anations. The rate constant for the bromide anation is kexp = k′[Br−]2 and for the chloride anation (in the presence of bromide) k′[Br−][Cl−] + k′' [Cl−]2. All reactions were followed using a stopped-flow technique at 25°C in 0.50M perchloric acid medium. The equilibrium constant for the redox equilibrium between Pt(CN)42−, iodine and Pt(CN)4I22− was determined separately to be (1.29 ± 0.03) × 104M−1.
Exploratory stopped-flow experiments indicate that the oxidative addition of chlorine to PtCl42− is first-order with respect to both chlorine and tetrachloroplatinate.
The experimental rate laws can be described by a reaction mechanism which resembles that introduced previously for Pt(II)-catalyzed anations and substitutions, in that both mechanisms can be considered as oxidative additions/reductive eliminations. (Less)
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organization
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type
Contribution to journal
publication status
published
subject
keywords
Oxidative addition, Reductive elimination, Platinum(II), Reaction mechanism, Halogen
in
Inorganica Chimica Acta
volume
19
issue
2
pages
7 pages
publisher
Elsevier
external identifiers
  • scopus:0001643536
ISSN
0020-1693
DOI
10.1016/S0020-1693(00)91090-9
language
English
LU publication?
yes
id
334d6cfb-bc1a-449e-b32b-8ad23be7f0e3
date added to LUP
2017-02-19 17:18:45
date last changed
2017-07-30 05:21:52
@article{334d6cfb-bc1a-449e-b32b-8ad23be7f0e3,
  abstract     = {The oxidative addition of iodine to Pt(CN)42− is first-order with respect to iodide, iodine and complex. The reverse reductive elimination of iodide from trans-Pt(CN)4I22- is first-order with respect to iodide and Pt(CN)4I22−. The kinetics for the reaction between bromide and trans-Pt(CN)4ClH2O2− involves a rate-determining reductive elimination of chloride, followed by a rapid oxidative addition of bromine to the formed Pt(CN)42−. The reactions between trans-Pt(CN)4BrH2O− and bromide or chloride can be described as halide assisted anations. The rate constant for the bromide anation is kexp = k′[Br−]2 and for the chloride anation (in the presence of bromide) k′[Br−][Cl−] + k′' [Cl−]2. All reactions were followed using a stopped-flow technique at 25°C in 0.50M perchloric acid medium. The equilibrium constant for the redox equilibrium between Pt(CN)42−, iodine and Pt(CN)4I22− was determined separately to be (1.29 ± 0.03) × 104M−1.<br/>     Exploratory stopped-flow experiments indicate that the oxidative addition of chlorine to PtCl42− is first-order with respect to both chlorine and tetrachloroplatinate.<br/>     The experimental rate laws can be described by a reaction mechanism which resembles that introduced previously for Pt(II)-catalyzed anations and substitutions, in that both mechanisms can be considered as oxidative additions/reductive eliminations.},
  author       = {Elding, Lars Ivar and Gustafson, Lena},
  issn         = {0020-1693},
  keyword      = {Oxidative addition,Reductive elimination,Platinum(II),Reaction mechanism,Halogen},
  language     = {eng},
  number       = {2},
  pages        = {165--171},
  publisher    = {Elsevier},
  series       = {Inorganica Chimica Acta},
  title        = {A Reaction Mechanism for Oxidative Addition of Halogen to Platinum(II), Reductive Elimination of Halide from Platinum(IV) and Halide Assisted Anations of Platinum(IV) Complexes},
  url          = {http://dx.doi.org/10.1016/S0020-1693(00)91090-9},
  volume       = {19},
  year         = {1976},
}