1H NMR Kinetic Study of Dimethyl Sulfoxide Exchange on Tetrakis(dimethyl- sulfoxide)platinum(II) at Variable Temperature and Pressure : High-pressure NMR kinetics. 36.
(1989) In Inorganic Chemistry 28(2). p.377-379- 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... (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:
https://lup.lub.lu.se/record/d1ae3475-3ebe-47c0-a80d-92fb4a0c560e
- author
- Ducommun, Yves ; Helm, Lothar ; Merbach, Andre E. ; Hellquist, Björn and Elding, Lars Ivar LU
- organization
- publishing date
- 1989-01
- 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 (ACS)
- external identifiers
-
- scopus:0001167278
- ISSN
- 1520-510X
- DOI
- 10.1021/ic00301a046
- language
- English
- LU publication?
- yes
- additional info
- 0020-1669/89/1328-0377
- id
- d1ae3475-3ebe-47c0-a80d-92fb4a0c560e
- date added to LUP
- 2017-01-09 16:07:13
- date last changed
- 2021-03-29 18:43:19
@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}}, keywords = {{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 (ACS)}}, 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}}, doi = {{10.1021/ic00301a046}}, volume = {{28}}, year = {{1989}}, }