The Solvent Path in Square-Planar Substitutions. Kinetics and Mechanism for Reactions of Tetrachloroplatinate(II) and Aquachloroplatinates(II) with Halides, Thiocyanate and Dimethyl Sulfoxide
(1978) In Inorganica Chimica Acta 31(2). p.243-250- Abstract
- The kinetics for the reactions between the six complexes PtCln(H2O)4-n−2n, n = 0,1,2,3,4 (including cis- and trans-isomers for n=2) and the entering ligands Y = Cl−, Br−, I−, SCN−, and DMSO have been studied. The experiments with PtCl42− and trans- PtCl2(H2O)2 give the usual two-term rate constant kexp = k1 + k2[Y], when no extra chloride has been added to the solutions. The parameter k1 can be identified as the acid hydrolysis rate constant for PtCl42− and trans-PtCl2(H2O)2, respectively. It is shown that both PtCl3H2O− and PtCl(H2O)3+ are sufficiently reactive for all Y to be the intermediates in the k1- paths of these two reactions. An associative process with the solvent is therefore probable.
The entering ligand order for H2O as... (More) - The kinetics for the reactions between the six complexes PtCln(H2O)4-n−2n, n = 0,1,2,3,4 (including cis- and trans-isomers for n=2) and the entering ligands Y = Cl−, Br−, I−, SCN−, and DMSO have been studied. The experiments with PtCl42− and trans- PtCl2(H2O)2 give the usual two-term rate constant kexp = k1 + k2[Y], when no extra chloride has been added to the solutions. The parameter k1 can be identified as the acid hydrolysis rate constant for PtCl42− and trans-PtCl2(H2O)2, respectively. It is shown that both PtCl3H2O− and PtCl(H2O)3+ are sufficiently reactive for all Y to be the intermediates in the k1- paths of these two reactions. An associative process with the solvent is therefore probable.
The entering ligand order for H2O as leaving ligand is DMSO < Cl− < Br− < SCN− < I− (approximately 0.3:1:4:40:100) for the substrate complexes studied. DMSO is a bad entering ligand in spite of its large trans-effect. The relative trans-effect Cl−/H2O and the relative efficacy of H2O and Cl− as leaving ligands depend on the nature of the entering ligand Y, whereas the relative cis-effect Cl-/H2O is independent of Y. This is compatible with an associative mechanism via a trigonal bipyramidal intermediate. (Less)
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- author
- Elding, Lars Ivar LU and Gröning, Ann-Britt
- organization
- publishing date
- 1978
- type
- Contribution to journal
- publication status
- published
- subject
- keywords
- Solvent path, Kinetics, Square-Planar complexes, Reaction mechanism, Platinum(II), Solvent path, Square-Planar complexes, Reaction mechanism, Kinetics, Platinum(II)
- in
- Inorganica Chimica Acta
- volume
- 31
- issue
- 2
- pages
- 8 pages
- publisher
- Elsevier
- external identifiers
-
- scopus:0006370762
- ISSN
- 0020-1693
- DOI
- 10.1016/S0020-1693(00)95010-2
- language
- English
- LU publication?
- yes
- id
- d5947864-e67c-4987-a85f-af381b977ee3
- date added to LUP
- 2017-02-13 16:33:38
- date last changed
- 2021-01-03 06:58:21
@article{d5947864-e67c-4987-a85f-af381b977ee3, abstract = {{The kinetics for the reactions between the six complexes PtCln(H2O)4-n−2n, n = 0,1,2,3,4 (including cis- and trans-isomers for n=2) and the entering ligands Y = Cl−, Br−, I−, SCN−, and DMSO have been studied. The experiments with PtCl42− and trans- PtCl2(H2O)2 give the usual two-term rate constant kexp = k1 + k2[Y], when no extra chloride has been added to the solutions. The parameter k1 can be identified as the acid hydrolysis rate constant for PtCl42− and trans-PtCl2(H2O)2, respectively. It is shown that both PtCl3H2O− and PtCl(H2O)3+ are sufficiently reactive for all Y to be the intermediates in the k1- paths of these two reactions. An associative process with the solvent is therefore probable.<br> The entering ligand order for H2O as leaving ligand is DMSO < Cl− < Br− < SCN− < I− (approximately 0.3:1:4:40:100) for the substrate complexes studied. DMSO is a bad entering ligand in spite of its large trans-effect. The relative trans-effect Cl−/H2O and the relative efficacy of H2O and Cl− as leaving ligands depend on the nature of the entering ligand Y, whereas the relative cis-effect Cl-/H2O is independent of Y. This is compatible with an associative mechanism via a trigonal bipyramidal intermediate.}}, author = {{Elding, Lars Ivar and Gröning, Ann-Britt}}, issn = {{0020-1693}}, keywords = {{Solvent path; Kinetics; Square-Planar complexes; Reaction mechanism; Platinum(II); Solvent path; Square-Planar complexes; Reaction mechanism; Kinetics; Platinum(II)}}, language = {{eng}}, number = {{2}}, pages = {{243--250}}, publisher = {{Elsevier}}, series = {{Inorganica Chimica Acta}}, title = {{The Solvent Path in Square-Planar Substitutions. Kinetics and Mechanism for Reactions of Tetrachloroplatinate(II) and Aquachloroplatinates(II) with Halides, Thiocyanate and Dimethyl Sulfoxide}}, url = {{http://dx.doi.org/10.1016/S0020-1693(00)95010-2}}, doi = {{10.1016/S0020-1693(00)95010-2}}, volume = {{31}}, year = {{1978}}, }