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Solvent Paths for Square-Planar Substitutions : Part 2. Reactions between Aqua Chloro-Platinates(II) and Ethene

Elding, Lars Ivar LU and Gröning, Ann-Britt (1980) In Inorganica Chimica Acta 38(1). p.59-66
Abstract (Swedish)
The kinetics for the reactions between the complexes PtCln(H2O)4-n 2−n, n = 0,1,2,3,4, (including cis- and trans-isomers for n=2) and ethene have been studied. In the case of trans-PtCl2(H2O)2, product analysis shows that both the chloride ligand and the aqua ligand are substituted by ethene in two parallel paths, differing in rate by a factor of only 1.5. The experiments show that ethene, and probably olefins in general, are inefficient entering ligands, similar to dimethyl sulfoxide. Steric reasons might be responsible. Changes in relative cis- and trans-effects are compatible with an associative mechanism. The aqua complexes are sufficiently reactive with ethene to be steady-state intermediates in associative solvent paths. Reaction... (More)
The kinetics for the reactions between the complexes PtCln(H2O)4-n 2−n, n = 0,1,2,3,4, (including cis- and trans-isomers for n=2) and ethene have been studied. In the case of trans-PtCl2(H2O)2, product analysis shows that both the chloride ligand and the aqua ligand are substituted by ethene in two parallel paths, differing in rate by a factor of only 1.5. The experiments show that ethene, and probably olefins in general, are inefficient entering ligands, similar to dimethyl sulfoxide. Steric reasons might be responsible. Changes in relative cis- and trans-effects are compatible with an associative mechanism. The aqua complexes are sufficiently reactive with ethene to be steady-state intermediates in associative solvent paths. Reaction models and rate laws for associative square-planar substitutions are discussed, with special reference to reported non-reactivity of solvento intermediates in some previously studied systems. (Less)
Abstract
The kinetics for the reactions between the complexes PtCln(H2O)4-n 2−n, n = 0,1,2,3,4, (including cis- and trans-isomers for n = 2) and ethene have been studied. In the case of trans-PtCl2(H2O)2, product analysis shows that both the chloride ligand and the aqua ligand are substituted by ethene in two parallel paths, differing in rate by a factor of 1.5 only. The experiments show that ethene, and probably olefins in general, are inefficient entering ligands, similar to dimethyl sulfoxide. Steric reasons might be responsible. Changes in relative cis- and trans-effects are compatible with an associative mechanism. The aqua complexes are sufficiently reactive with ethene to be steady-state intermediates in associative solvent paths. Reaction... (More)
The kinetics for the reactions between the complexes PtCln(H2O)4-n 2−n, n = 0,1,2,3,4, (including cis- and trans-isomers for n = 2) and ethene have been studied. In the case of trans-PtCl2(H2O)2, product analysis shows that both the chloride ligand and the aqua ligand are substituted by ethene in two parallel paths, differing in rate by a factor of 1.5 only. The experiments show that ethene, and probably olefins in general, are inefficient entering ligands, similar to dimethyl sulfoxide. Steric reasons might be responsible. Changes in relative cis- and trans-effects are compatible with an associative mechanism. The aqua complexes are sufficiently reactive with ethene to be steady-state intermediates in associative solvent paths. Reaction models and rate laws for associative square-planar substitutions are discussed, with special reference to reported non-reactivity of solvento intermediates in some previously studied systems. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Solvent path, Aqua chloro platinate, Substitution reactions, Reaction mechanism, Square-planar complex
in
Inorganica Chimica Acta
volume
38
issue
1
pages
8 pages
publisher
Elsevier
external identifiers
  • scopus:0002486091
ISSN
0020-1693
DOI
10.1016/S0020-1693(00)91935-2
language
English
LU publication?
yes
id
ce40d49e-dfc6-47da-b8d4-d8d6a6c3fc0e
date added to LUP
2017-02-13 16:02:06
date last changed
2017-07-30 05:21:26
@article{ce40d49e-dfc6-47da-b8d4-d8d6a6c3fc0e,
  abstract     = {The kinetics for the reactions between the complexes PtCln(H2O)4-n 2−n, n = 0,1,2,3,4, (including cis- and trans-isomers for n = 2) and ethene have been studied. In the case of trans-PtCl2(H2O)2, product analysis shows that both the chloride ligand and the aqua ligand are substituted by ethene in two parallel paths, differing in rate by a factor of 1.5 only. The experiments show that ethene, and probably olefins in general, are inefficient entering ligands, similar to dimethyl sulfoxide. Steric reasons might be responsible. Changes in relative cis- and trans-effects are compatible with an associative mechanism. The aqua complexes are sufficiently reactive with ethene to be steady-state intermediates in associative solvent paths. Reaction models and rate laws for associative square-planar substitutions are discussed, with special reference to reported non-reactivity of solvento intermediates in some previously studied systems.},
  author       = {Elding, Lars Ivar and Gröning, Ann-Britt},
  issn         = {0020-1693},
  keyword      = {Solvent path,Aqua chloro platinate,Substitution reactions,Reaction mechanism,Square-planar complex},
  language     = {eng},
  number       = {1},
  pages        = {59--66},
  publisher    = {Elsevier},
  series       = {Inorganica Chimica Acta},
  title        = {Solvent Paths for Square-Planar Substitutions : Part 2. Reactions between Aqua Chloro-Platinates(II) and Ethene},
  url          = {http://dx.doi.org/10.1016/S0020-1693(00)91935-2},
  volume       = {38},
  year         = {1980},
}