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
(1976) In Inorganica Chimica Acta 19(2). p.165-171- 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) - 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)
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https://lup.lub.lu.se/record/334d6cfb-bc1a-449e-b32b-8ad23be7f0e3
- author
- Elding, Lars Ivar LU and Gustafson, Lena
- organization
- publishing date
- 1976
- 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
- 2021-01-03 09:18:23
@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}}, keywords = {{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}}, doi = {{10.1016/S0020-1693(00)91090-9}}, volume = {{19}}, year = {{1976}}, }