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Dinuclear complexes contributing to softness of metal acceptors

Fronaeus, Sture LU (2004) In Journal of Solution Chemistry 33(8). p.975-994
Abstract
Since emf measurements with amalgam electrodes have been used, in most studies of the stabilities of complexes between soft metal acceptors and halide ions a series of investigations of the kinetics of electrode reactions were accomplished with halide systems of metal ions in the Groups 11 and 12 in aqueous and/or DMSO solutions. The aim was to establish which complexes contribute to the exchange current density, i(o). Such measurements are found to be a very sensitive method for identifying dinuclear complexes that can display much higher charge transfer rate constants than mononuclear complexes can. From these results it can be stated that hard acceptors do not show any tendency to form dinuclear halide complexes, whereas soft acceptors... (More)
Since emf measurements with amalgam electrodes have been used, in most studies of the stabilities of complexes between soft metal acceptors and halide ions a series of investigations of the kinetics of electrode reactions were accomplished with halide systems of metal ions in the Groups 11 and 12 in aqueous and/or DMSO solutions. The aim was to establish which complexes contribute to the exchange current density, i(o). Such measurements are found to be a very sensitive method for identifying dinuclear complexes that can display much higher charge transfer rate constants than mononuclear complexes can. From these results it can be stated that hard acceptors do not show any tendency to form dinuclear halide complexes, whereas soft acceptors are apt to do so. This fact leads to the conclusion that dinuclear complexes have a strong internuclear bond. In determinations of the overall stability constant beta(j) of a complex MLj there is an influence from a complex M2Lj with a constant beta(j)', resulting in the substitution of beta(j) for (beta(j) + 2a(j) beta(j)'), where a(j) = [M] when the ligand number n = (C-L - [L])/C-M has the value j. An approximate value of the association constant, K-ass, of the internuclear bond can be calculated from beta(j)' if beta(j) is known. On the basis of these measurements the most probable types of the internuclear bonds are discussed. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
association constant, dinuclear complexes, electrode kinetics, exchange current density i(0), internuclear bond
in
Journal of Solution Chemistry
volume
33
issue
8
pages
975 - 994
publisher
Springer
external identifiers
  • wos:000225065300004
  • scopus:8744239489
ISSN
1572-8927
DOI
10.1023/B:JOSL.0000048048.11035.02
language
English
LU publication?
yes
id
41a473f0-102e-4b89-9e5b-5d662a89a76c (old id 260877)
date added to LUP
2007-10-22 19:04:56
date last changed
2017-01-01 04:52:05
@article{41a473f0-102e-4b89-9e5b-5d662a89a76c,
  abstract     = {Since emf measurements with amalgam electrodes have been used, in most studies of the stabilities of complexes between soft metal acceptors and halide ions a series of investigations of the kinetics of electrode reactions were accomplished with halide systems of metal ions in the Groups 11 and 12 in aqueous and/or DMSO solutions. The aim was to establish which complexes contribute to the exchange current density, i(o). Such measurements are found to be a very sensitive method for identifying dinuclear complexes that can display much higher charge transfer rate constants than mononuclear complexes can. From these results it can be stated that hard acceptors do not show any tendency to form dinuclear halide complexes, whereas soft acceptors are apt to do so. This fact leads to the conclusion that dinuclear complexes have a strong internuclear bond. In determinations of the overall stability constant beta(j) of a complex MLj there is an influence from a complex M2Lj with a constant beta(j)', resulting in the substitution of beta(j) for (beta(j) + 2a(j) beta(j)'), where a(j) = [M] when the ligand number n = (C-L - [L])/C-M has the value j. An approximate value of the association constant, K-ass, of the internuclear bond can be calculated from beta(j)' if beta(j) is known. On the basis of these measurements the most probable types of the internuclear bonds are discussed.},
  author       = {Fronaeus, Sture},
  issn         = {1572-8927},
  keyword      = {association constant,dinuclear complexes,electrode kinetics,exchange current density i(0),internuclear bond},
  language     = {eng},
  number       = {8},
  pages        = {975--994},
  publisher    = {Springer},
  series       = {Journal of Solution Chemistry},
  title        = {Dinuclear complexes contributing to softness of metal acceptors},
  url          = {http://dx.doi.org/10.1023/B:JOSL.0000048048.11035.02},
  volume       = {33},
  year         = {2004},
}