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A Reaction Mechanis...
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
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- Elding, Lars Ivar (författare)
- Lund University,Lunds universitet,Centrum för analys och syntes,Kemiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Centre for Analysis and Synthesis,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH
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- Gustafson, Lena (författare)
- Lund University
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(creator_code:org_t)
- 1976
- 1976
- Engelska 7 s.
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Ingår i: Inorganica Chimica Acta. - 0020-1693. ; 19:2, s. 165-171
- Relaterad länk:
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http://dx.doi.org/10...
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https://lup.lub.lu.s...
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https://doi.org/10.1...
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Abstract
Ämnesord
Stäng
- 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.
- 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.
Ämnesord
- NATURVETENSKAP -- Kemi -- Oorganisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Inorganic Chemistry (hsv//eng)
Nyckelord
- Oxidative addition
- Reductive elimination
- Platinum(II)
- Reaction mechanism
- Halogen
Publikations- och innehållstyp
- art (ämneskategori)
- ref (ämneskategori)
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