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1H NMR Kinetic Study of Dimethyl Sulfoxide Exchange on Tetrakis(dimethyl- sulfoxide)platinum(II) at Variable Temperature and Pressure : High-pressure NMR kinetics. 36.

Ducommun, Yves; Helm, Lothar; Merbach, Andre E.; Hellquist, Björn and Elding, Lars Ivar LU (1989) In Inorganic Chemistry 28(2). p.377-379
Abstract (Swedish)
The present report is a 'H NMR investigation of the dimethyl sulfoxide exchange on Pt(Me2S0)42+ as a function of temperature and pressure in CD3N02. Dimethyl sulfoxide is an ambidentate ligand, and the complex contains two 0-bonded and two S-bonded ligands that are exchanging with the free ligand at different rates. It is favorable to follow these exchanges in a non-coordinating diluent like nitromethane, since it allows variation of the ligand concentration, thus giving an opportunity to establish the rate law. The use of a diluent of high dielectric constant and of uncharged ligands minimizes the electrostriction changes along the reaction path, so that the measured volumes of activation will reflect primarily the intrinsic changes of... (More)
The present report is a 'H NMR investigation of the dimethyl sulfoxide exchange on Pt(Me2S0)42+ as a function of temperature and pressure in CD3N02. Dimethyl sulfoxide is an ambidentate ligand, and the complex contains two 0-bonded and two S-bonded ligands that are exchanging with the free ligand at different rates. It is favorable to follow these exchanges in a non-coordinating diluent like nitromethane, since it allows variation of the ligand concentration, thus giving an opportunity to establish the rate law. The use of a diluent of high dielectric constant and of uncharged ligands minimizes the electrostriction changes along the reaction path, so that the measured volumes of activation will reflect primarily the intrinsic changes of molecular volumes on going to the transition state. (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
Proton NMR, Dimethyl sulfoxide, Exchange reaction, Platinum(II), Reaction mechanism, Activation entropy, Activation volume, Fast kinetics, High pressure kinetics
in
Inorganic Chemistry
volume
28
issue
2
pages
377 - 379
publisher
The American Chemical Society
external identifiers
  • scopus:0001167278
ISSN
1520-510X
DOI
10.1021/ic00301a046
language
English
LU publication?
yes
id
d1ae3475-3ebe-47c0-a80d-92fb4a0c560e
date added to LUP
2017-01-09 16:07:13
date last changed
2017-07-30 05:19:58
@article{d1ae3475-3ebe-47c0-a80d-92fb4a0c560e,
  abstract     = {The present report is a 'H NMR investigation of the dimethyl sulfoxide exchange on Pt(Me2S0)42+ as a function of temperature and pressure in CD3N02. Dimethyl sulfoxide is an ambidentate ligand, and the complex contains two 0-bonded and two S-bonded ligands that are exchanging with the free ligand at different rates. It is favorable to follow these exchanges in a non-coordinating diluent like nitromethane, since it allows variation of the ligand concentration, thus giving an opportunity to establish the rate law. The use of a diluent of high dielectric constant and of uncharged ligands minimizes the electrostriction changes along the reaction path, so that the measured volumes of activation will reflect primarily the intrinsic changes of molecular volumes on going to the transition state.},
  author       = {Ducommun, Yves and Helm, Lothar and Merbach, Andre E. and Hellquist, Björn  and Elding, Lars Ivar},
  issn         = {1520-510X},
  keyword      = {Proton NMR,Dimethyl sulfoxide,Exchange reaction,Platinum(II),Reaction mechanism,Activation entropy,Activation volume,Fast kinetics,High pressure kinetics},
  language     = {eng},
  number       = {2},
  pages        = {377--379},
  publisher    = {The American Chemical Society},
  series       = {Inorganic Chemistry},
  title        = {1H NMR Kinetic Study of Dimethyl Sulfoxide Exchange on Tetrakis(dimethyl- sulfoxide)platinum(II) at Variable Temperature and Pressure : High-pressure NMR kinetics. 36.},
  url          = {http://dx.doi.org/10.1021/ic00301a046},
  volume       = {28},
  year         = {1989},
}