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The trans effect and trans influence of triphenyl arsine in platinum(II) complexes. A comparative mechanistic and structural study

Kuznik, N and Wendt, Ola LU (2002) In Journal of the Chemical Society. Dalton Transactions p.3074-3078
Abstract
The kinetics and mechanism of the reaction between [PtI3(AsPh3)](-) and pyridine in acetonitrile solvent has been studied by use of stopped-flow spectrophotometry. Substitution of iodide trans to arsine is irreversible under the conditions used and takes place via parallel direct and solvolytic pathways. By comparing the rate constants of the direct pathway with literature values of the corresponding phosphine and stibine complexes the following trans effect series can be obtained: Ph3Sb > Ph3P > Ph3As. The crystal and molecular structures of reactant and product have been determined. Based on Pt-I distances for the investigated arsine complex and literature data for the corresponding phosphine and stibine complexes the following... (More)
The kinetics and mechanism of the reaction between [PtI3(AsPh3)](-) and pyridine in acetonitrile solvent has been studied by use of stopped-flow spectrophotometry. Substitution of iodide trans to arsine is irreversible under the conditions used and takes place via parallel direct and solvolytic pathways. By comparing the rate constants of the direct pathway with literature values of the corresponding phosphine and stibine complexes the following trans effect series can be obtained: Ph3Sb > Ph3P > Ph3As. The crystal and molecular structures of reactant and product have been determined. Based on Pt-I distances for the investigated arsine complex and literature data for the corresponding phosphine and stibine complexes the following trans influence series was derived: Ph3P greater than or equal to Ph3As > Ph3Sb. To the best of our knowledge this is the first comparison of all the three heavier pnictogens as donor atoms using strictly analogous complexes with identical cis-ligands. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of the Chemical Society. Dalton Transactions
issue
15
pages
3074 - 3078
publisher
Royal Society of Chemistry
external identifiers
  • wos:000176981400022
  • scopus:0035982509
ISSN
1472-7773
DOI
10.1039/b202100p
language
English
LU publication?
yes
id
b43d8ce6-0dac-4e60-928c-2f85c4af5970 (old id 332660)
date added to LUP
2007-11-05 14:14:39
date last changed
2017-08-27 05:36:03
@article{b43d8ce6-0dac-4e60-928c-2f85c4af5970,
  abstract     = {The kinetics and mechanism of the reaction between [PtI3(AsPh3)](-) and pyridine in acetonitrile solvent has been studied by use of stopped-flow spectrophotometry. Substitution of iodide trans to arsine is irreversible under the conditions used and takes place via parallel direct and solvolytic pathways. By comparing the rate constants of the direct pathway with literature values of the corresponding phosphine and stibine complexes the following trans effect series can be obtained: Ph3Sb > Ph3P > Ph3As. The crystal and molecular structures of reactant and product have been determined. Based on Pt-I distances for the investigated arsine complex and literature data for the corresponding phosphine and stibine complexes the following trans influence series was derived: Ph3P greater than or equal to Ph3As > Ph3Sb. To the best of our knowledge this is the first comparison of all the three heavier pnictogens as donor atoms using strictly analogous complexes with identical cis-ligands.},
  author       = {Kuznik, N and Wendt, Ola},
  issn         = {1472-7773},
  language     = {eng},
  number       = {15},
  pages        = {3074--3078},
  publisher    = {Royal Society of Chemistry},
  series       = {Journal of the Chemical Society. Dalton Transactions},
  title        = {The trans effect and trans influence of triphenyl arsine in platinum(II) complexes. A comparative mechanistic and structural study},
  url          = {http://dx.doi.org/10.1039/b202100p},
  year         = {2002},
}