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Palladium(II) Halid...
Palladium(II) Halide Complexes III. Acid Hydrolyses and Halide Anations of cis- and trans-Dichlorodiaquapalladium(II) and -Dibromoaquapalladium(II))
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- Elding, Lars Ivar (author)
- 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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(creator_code:org_t)
- 1973
- 1973
- English 8 s.
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In: Inorganica Chimica Acta. - 0020-1693. ; 7, s. 581-588
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Abstract
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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
- NATURVETENSKAP -- Kemi -- Oorganisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Inorganic Chemistry (hsv//eng)
Keyword
- Palladium(II)
- Halide complex
- Acid hydrolysis
- Halide anation
- Reaction mechanism
- Activation parameters
- trans-effect
- cis-effect
- cis/trans equilibrium
Publication and Content Type
- art (subject category)
- ref (subject category)
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