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Palladium(II) Halide Complexes III. Acid Hydrolyses and Halide Anations of cis- and trans-Dichlorodiaquapalladium(II) and -Dibromoaquapalladium(II))

Elding, Lars Ivar LU (1973) In Inorganica Chimica Acta 7. p.581-588
Abstract
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... (More)
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. (Less)
Abstract (Swedish)
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... (More)
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. (Less)
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author
organization
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type
Contribution to journal
publication status
published
subject
keywords
Palladium(II), Halide complex, Acid hydrolysis, Halide anation, Reaction mechanism, Activation parameters, trans-effect, cis-effect, cis/trans equilibrium
in
Inorganica Chimica Acta
volume
7
pages
8 pages
publisher
Elsevier
external identifiers
  • scopus:0000008603
ISSN
0020-1693
DOI
10.1016/S0020-1693(00)94890-4
language
English
LU publication?
yes
id
cb4fe4f3-823c-4d79-b858-85110a7c3bcc
date added to LUP
2017-02-19 19:02:32
date last changed
2021-04-25 05:08:15
@article{cb4fe4f3-823c-4d79-b858-85110a7c3bcc,
  abstract     = {{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.<br/>       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.}},
  author       = {{Elding, Lars Ivar}},
  issn         = {{0020-1693}},
  keywords     = {{Palladium(II); Halide complex; Acid hydrolysis; Halide anation; Reaction mechanism; Activation parameters; trans-effect; cis-effect; cis/trans equilibrium}},
  language     = {{eng}},
  pages        = {{581--588}},
  publisher    = {{Elsevier}},
  series       = {{Inorganica Chimica Acta}},
  title        = {{Palladium(II) Halide Complexes III. Acid Hydrolyses and Halide Anations of cis- and trans-Dichlorodiaquapalladium(II) and -Dibromoaquapalladium(II))}},
  url          = {{http://dx.doi.org/10.1016/S0020-1693(00)94890-4}},
  doi          = {{10.1016/S0020-1693(00)94890-4}},
  volume       = {{7}},
  year         = {{1973}},
}