Kinetics and Mechanism for Reduction of Gold(III) Complexes by Dimethylsulfide
(1997) In Journal of the Chemical Society. Dalton Transactions 1997(7). p.1159-1164- 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)
- 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)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/e0dd8377-ac77-408b-8c3b-91b019cfb1e6
- author
- Ericson, Anna LU ; Elding, Lars Ivar LU and Elmroth, Sofi K. C. LU
- organization
- publishing date
- 1997-04-07
- 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
- external identifiers
-
- scopus:33748814003
- 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
- 2022-03-16 19:08:24
@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}},
keywords = {{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}},
doi = {{10.1039/a608001d}},
volume = {{1997}},
year = {{1997}},
}