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- Elding, Lars IvarLund 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 (author)
Palladium(II) Halide Complexes III. Acid Hydrolyses and Halide Anations of cis- and trans-Dichlorodiaquapalladium(II) and -Dibromoaquapalladium(II))
- Article/chapterEnglish1973
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- 1973
- 8 s.
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- LIBRIS-ID:oai:lup.lub.lu.se:cb4fe4f3-823c-4d79-b858-85110a7c3bcc
- https://lup.lub.lu.se/record/cb4fe4f3-823c-4d79-b858-85110a7c3bccURI
- https://doi.org/10.1016/S0020-1693(00)94890-4DOI
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- Language:English
- Summary in:English &Swedish
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- Chloride and bromide anations of PdX(H2O)3+, cis-PdX2(H2O)2 and trans-PdX2(H2O)2, acid hydrolyses of PdX3H2O−, cis-PdX2(H2O)2 and trans-PcX2(H2O)2, X = Cl, Br, have been studied at different temperatures by means of a stopped-flow technique. Rate constants and activation parameters are given. The palladium complexes react about 5×104 to 5×105 times faster than the analogous platinum(II) complexes. The activation enthalpies are 8 to 10 kcal mol−1 smaller for palladium. A simple model for description of the rates of acid hydrolyses and halide anations of palladium(II) and platinum(II) halide complexes by cis-, trans-, and ionic charge effects is introduced. For palladium, the relative trans-effect Cl/H2O is about 50 and Br/H2O about 500. The relative cis-effect H2O/ Cl is about 4 and H2O/Br about 8. The trans-effects are 6 times smaller than for corresponding platinum complexes, the cis-effects somewhat greater. The equilibrium between cis-PdX2(H2O)2 and trans-PdX2(H2O)2 has been studied. The cis-isomer is the predominant species at equilibrium, the equilibrium constant cis/trans being 2.1±0.3 for X = Cl and 6.0± 0.8 for X = Br at 25°C. The ionic strength was 1.00 M and the supporting electrolyte perchloric acid.
- Chloride and bromide anations of PdX(H2O)3+, cis-PdX2(H2O)2 and trans-PdX2(H2O)2, acid hydrolyses of PdX3H2O−, cis-PdX2(H2O)2 and trans-PcX2(H2O)2, X = Cl, Br, have been studied at different temperatures by means of a stopped-flow technique. Rate constants and activation parameters are given. The palladium complexes react about 5×104 to 5×105 times faster than the analogous platinum(II) complexes. The activation enthalpies are 8 to 10 kcal mol−1 smaller for palladium. A simple model for description of the rates of acid hydrolyses and halide anations of palladium(II) and platinum(II) halide complexes by cis-, trans-, and ionic charge effects is introduced. For palladium, the relative trans-effect Cl/H2O is about 50 and Br/H2O about 500. The relative cis-effect H2O/ Cl is about 4 and H2O/Br about 8. The trans-effects are 6 times smaller than for corresponding platinum complexes, the cis-effects somewhat greater. The equilibrium between cis-PdX2(H2O)2 and trans-PdX2(H2O)2 has been studied. The cis-isomer is the predominant species at equilibrium, the equilibrium constant cis/trans being 2.1±0.3 for X = Cl and 6.0± 0.8 for X = Br at 25°C. The ionic strength was 1.00 M and the supporting electrolyte perchloric acid.
Subject headings and genre
- NATURVETENSKAP Kemi Oorganisk kemi hsv//swe
- NATURAL SCIENCES Chemical Sciences Inorganic Chemistry hsv//eng
- Palladium(II)
- Halide complex
- Acid hydrolysis
- Halide anation
- Reaction mechanism
- Activation parameters
- trans-effect
- cis-effect
- cis/trans equilibrium
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- Centrum för analys och syntesKemiska institutionen (creator_code:org_t)
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- In:Inorganica Chimica Acta7, s. 581-5880020-1693
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