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Kinetics and Mechanism for Reduction of Gold(III) Complexes by Dimethylsulfide

Ericson, Anna LU ; Elding, Lars Ivar LU and Elmroth, Sofi K. C. LU (1997) In Journal of the Chemical Society. Dalton Transactions 1997(7). p.1159-1164
Abstract (Swedish)
The reactions between trans-[Au(CN) 2 X 2 ] - (X = Cl or Br) and Me 2 S have been studied by conventional and high-pressure stopped-flow spectrophotometry in acidic aqueous solution containing 10% (w/w) methanol. The overall stoichiometry Au III ∶Me 2 S is 1∶(1.0 ± 0.1) in agreement with the reaction: trans-[Au(CN) 2 X 2 ] - + Me 2 S + H 2 O → [Au(CN) 2 ] - + Me 2 SO + 2H + + 2X - . Initial rapid substitution processes result in the formation of a pre-equilibrium between transient gold(III) complexes, which are reduced to [Au(CN) 2 ] - in a subsequent slower redox process. Complexes trans-[Au(CN) 2 X(Me 2 S)] with an asymmetric electron distribution along the X–Au–S axis are reduced rapidly via an intermolecular process, in which Me 2 S... (More)
The reactions between trans-[Au(CN) 2 X 2 ] - (X = Cl or Br) and Me 2 S have been studied by conventional and high-pressure stopped-flow spectrophotometry in acidic aqueous solution containing 10% (w/w) methanol. The overall stoichiometry Au III ∶Me 2 S is 1∶(1.0 ± 0.1) in agreement with the reaction: trans-[Au(CN) 2 X 2 ] - + Me 2 S + H 2 O → [Au(CN) 2 ] - + Me 2 SO + 2H + + 2X - . Initial rapid substitution processes result in the formation of a pre-equilibrium between transient gold(III) complexes, which are reduced to [Au(CN) 2 ] - in a subsequent slower redox process. Complexes trans-[Au(CN) 2 X(Me 2 S)] with an asymmetric electron distribution along the X–Au–S axis are reduced rapidly via an intermolecular process, in which Me 2 S attacks a co-ordinated halide. The complex trans-[Au(CN) 2 (Me 2 S) 2 ] , on the other hand, undergoes slow reduction to gold(I) involving a water molecule. The rapid halide-mediated oxidation of thioethers implies that reduction of metal ions in biological systems by such moieties should be favoured in extracellular environments, where the chloride concentrations are high. (Less)
Abstract
The reactions between trans-[Au(CN) 2 X 2 ] - (X = Cl or Br) and Me 2 S have been studied by conventional and high-pressure stopped-flow spectrophotometry in acidic aqueous solution containing 10% (w/w) methanol. The overall stoichiometry Au III ∶Me 2 S is 1∶(1.0 ± 0.1) in agreement with the reaction: trans-[Au(CN) 2 X 2 ] - + Me 2 S + H 2 O → [Au(CN) 2 ] - + Me 2 SO + 2H + + 2X - . Initial rapid substitution processes result in the formation of a pre-equilibrium between transient gold(III) complexes, which are reduced to [Au(CN) 2 ] - in a subsequent slower redox process. Complexes trans-[Au(CN) 2 X(Me 2 S)] with an asymmetric electron distribution along the X–Au–S axis are reduced rapidly via an intermolecular process, in which Me 2 S... (More)
The reactions between trans-[Au(CN) 2 X 2 ] - (X = Cl or Br) and Me 2 S have been studied by conventional and high-pressure stopped-flow spectrophotometry in acidic aqueous solution containing 10% (w/w) methanol. The overall stoichiometry Au III ∶Me 2 S is 1∶(1.0 ± 0.1) in agreement with the reaction: trans-[Au(CN) 2 X 2 ] - + Me 2 S + H 2 O → [Au(CN) 2 ] - + Me 2 SO + 2H + + 2X - . Initial rapid substitution processes result in the formation of a pre-equilibrium between transient gold(III) complexes, which are reduced to [Au(CN) 2 ] - in a subsequent slower redox process. Complexes trans-[Au(CN) 2 X(Me 2 S)] with an asymmetric electron distribution along the X–Au–S axis are reduced rapidly via an intermolecular process, in which Me 2 S attacks a co-ordinated halide. The complex trans-[Au(CN) 2 (Me 2 S) 2 ] , on the other hand, undergoes slow reduction to gold(I) involving a water molecule. The rapid halide-mediated oxidation of thioethers implies that reduction of metal ions in biological systems by such moieties should be favoured in extracellular environments, where the chloride concentrations are high. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Gold(iii) complexes, Dimethylsulfide, Reduction, High-pressure kinetics, Fast kinetics, Reaction mechanism, Halide-mediated oxidation of thioethers
in
Journal of the Chemical Society. Dalton Transactions
volume
1997
issue
7
pages
6 pages
publisher
Royal Society of Chemistry
ISSN
1472-7773
DOI
10.1039/a608001d
language
English
LU publication?
yes
id
e0dd8377-ac77-408b-8c3b-91b019cfb1e6
date added to LUP
2017-01-04 11:09:37
date last changed
2017-03-28 12:09:57
@article{e0dd8377-ac77-408b-8c3b-91b019cfb1e6,
  abstract     = {The reactions between trans-[Au(CN) 2 X 2 ] - (X = Cl or Br) and Me 2 S have been studied by conventional and high-pressure stopped-flow spectrophotometry in acidic aqueous solution containing 10% (w/w) methanol. The overall stoichiometry Au III ∶Me 2 S is 1∶(1.0 ± 0.1) in agreement with the reaction: trans-[Au(CN) 2 X 2 ] - + Me 2 S + H 2 O → [Au(CN) 2 ] - + Me 2 SO + 2H + + 2X - . Initial rapid substitution processes result in the formation of a pre-equilibrium between transient gold(III) complexes, which are reduced to [Au(CN) 2 ] - in a subsequent slower redox process. Complexes trans-[Au(CN) 2 X(Me 2 S)] with an asymmetric electron distribution along the X–Au–S axis are reduced rapidly via an intermolecular process, in which Me 2 S attacks a co-ordinated halide. The complex trans-[Au(CN) 2 (Me 2 S) 2 ] , on the other hand, undergoes slow reduction to gold(I) involving a water molecule. The rapid halide-mediated oxidation of thioethers implies that reduction of metal ions in biological systems by such moieties should be favoured in extracellular environments, where the chloride concentrations are high. },
  author       = {Ericson, Anna and Elding, Lars Ivar and Elmroth, Sofi K. C.},
  issn         = {1472-7773},
  keyword      = {Gold(iii) complexes,Dimethylsulfide,Reduction,High-pressure kinetics,Fast kinetics,Reaction mechanism,Halide-mediated oxidation of thioethers},
  language     = {eng},
  month        = {04},
  number       = {7},
  pages        = {1159--1164},
  publisher    = {Royal Society of Chemistry},
  series       = {Journal of the Chemical Society. Dalton Transactions},
  title        = {Kinetics and Mechanism for Reduction of Gold(III) Complexes by Dimethylsulfide},
  url          = {http://dx.doi.org/10.1039/a608001d},
  volume       = {1997},
  year         = {1997},
}