Advanced

Palladium(II) Halide Complexes II. Acid Hydrolysis and Halide Anations of Palladium(II) Chloro and Bromo Aqua Complexes

Elding, Lars Ivar LU (1972) In Inorganica Chimica Acta 6. p.683-688
Abstract (Swedish)
The rate constants for the chloride and bromide anations of Pd(H2O)42+, the chloride anations of PdCl3H2O−, the bromide anation of PdBr3H2O− and the acid hydrolysis of PdCl(H2O)3+, PdBr(H2O)3+, PdCl42−, and PdBr42− have been determined at 15, 25 and 35 °C using a stopped-flow technique. The ionic strength was 1.00 M and the supporting electrolyte perchloric acid. The obtained rate constants and the activation enthalpies and entropies are given. A comparison with the corresponding reactions for platinum(II) complexes indicates that the acid hydrolyses are 1×105 to 2×105 times faster and the halide anations 4×101 to 6×104 times faster for palladium. The increased rates of reaction are due to a decrease in activation enthalpies. The reactions... (More)
The rate constants for the chloride and bromide anations of Pd(H2O)42+, the chloride anations of PdCl3H2O−, the bromide anation of PdBr3H2O− and the acid hydrolysis of PdCl(H2O)3+, PdBr(H2O)3+, PdCl42−, and PdBr42− have been determined at 15, 25 and 35 °C using a stopped-flow technique. The ionic strength was 1.00 M and the supporting electrolyte perchloric acid. The obtained rate constants and the activation enthalpies and entropies are given. A comparison with the corresponding reactions for platinum(II) complexes indicates that the acid hydrolyses are 1×105 to 2×105 times faster and the halide anations 4×101 to 6×104 times faster for palladium. The increased rates of reaction are due to a decrease in activation enthalpies. The reactions are typically square planar substitutions with respect to entering and leaving groups. The mechanism appears to be associative in nature. (Less)
Abstract
The rate constants for the chloride and bromide anations of Pd(H2O)42+, the chloride anations of PdCl3H2O−, the bromide anation of PdBr3H2O− and the acid hydrolysis of PdCl(H2O)3+, PdBr(H2O)3+, PdCl42−, and PdBr42− have been determined at 15, 25 and 35 °C using a stopped-flow technique. The ionic strength was 1.00 M and the supporting electrolyte perchloric acid. The obtained rate constants and the activation enthalpies and entropies are given. A comparison with the corresponding reactions for platinum(II) complexes indicates that the acid hydrolyses are 1×105 to 2×105 times faster and the halide anations 4×101 to 6×104 times faster for palladium. The increased rates of reaction are due to a decrease in activation enthalpies. The reactions... (More)
The rate constants for the chloride and bromide anations of Pd(H2O)42+, the chloride anations of PdCl3H2O−, the bromide anation of PdBr3H2O− and the acid hydrolysis of PdCl(H2O)3+, PdBr(H2O)3+, PdCl42−, and PdBr42− have been determined at 15, 25 and 35 °C using a stopped-flow technique. The ionic strength was 1.00 M and the supporting electrolyte perchloric acid. The obtained rate constants and the activation enthalpies and entropies are given. A comparison with the corresponding reactions for platinum(II) complexes indicates that the acid hydrolyses are 1×105 to 2×105 times faster and the halide anations 4×101 to 6×104 times faster for palladium. The increased rates of reaction are due to a decrease in activation enthalpies. The reactions are typically square planar substitutions with respect to entering and leaving groups. The mechanism appears to be associative in nature. (Less)
Please use this url to cite or link to this publication:
author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Acid hydrolysis, Halide anation, Palladium(II) complexes, Stopped-flow kinetics, Activation parameters, Associative reactions
in
Inorganica Chimica Acta
volume
6
pages
7 pages
publisher
Elsevier
external identifiers
  • scopus:0004373473
ISSN
0020-1693
DOI
10.1016/S0020-1693(00)91884-X
language
English
LU publication?
yes
id
b69b853a-88e8-4839-a01c-c4340516fb76
date added to LUP
2017-02-19 19:14:54
date last changed
2017-11-12 04:29:35
@article{b69b853a-88e8-4839-a01c-c4340516fb76,
  abstract     = {The rate constants for the chloride and bromide anations of Pd(H2O)42+, the chloride anations of PdCl3H2O−, the bromide anation of PdBr3H2O− and the acid hydrolysis of PdCl(H2O)3+, PdBr(H2O)3+, PdCl42−, and PdBr42− have been determined at 15, 25 and 35 °C using a stopped-flow technique. The ionic strength was 1.00 M and the supporting electrolyte perchloric acid. The obtained rate constants and the activation enthalpies and entropies are given. A comparison with the corresponding reactions for platinum(II) complexes indicates that the acid hydrolyses are 1×105 to 2×105 times faster and the halide anations 4×101 to 6×104 times faster for palladium. The increased rates of reaction are due to a decrease in activation enthalpies. The reactions are typically square planar substitutions with respect to entering and leaving groups. The mechanism appears to be associative in nature.},
  author       = {Elding, Lars Ivar},
  issn         = {0020-1693},
  keyword      = {Acid hydrolysis,Halide anation,Palladium(II) complexes,Stopped-flow kinetics,Activation parameters,Associative reactions},
  language     = {eng},
  pages        = {683--688},
  publisher    = {Elsevier},
  series       = {Inorganica Chimica Acta},
  title        = {Palladium(II) Halide Complexes II. Acid Hydrolysis and Halide Anations of Palladium(II) Chloro and Bromo Aqua Complexes},
  url          = {http://dx.doi.org/10.1016/S0020-1693(00)91884-X},
  volume       = {6},
  year         = {1972},
}