The trans effect and trans influence of triphenyl arsine in platinum(II) complexes. A comparative mechanistic and structural study
(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)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/332660
- author
- Kuznik, N and Wendt, Ola LU
- organization
- publishing date
- 2002
- 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
- 2016-04-01 16:55:47
- date last changed
- 2022-02-05 19:31:09
@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}}, doi = {{10.1039/b202100p}}, year = {{2002}}, }