Endre søk
RefereraExporteraLink to record
Permanent link

Direct link
Referera
Referensformat
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Annet format
Fler format
Språk
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Annet språk
Fler språk
Utmatningsformat
  • html
  • text
  • asciidoc
  • rtf
New class of oligonuclear platinum-thallium compounds with a direct metal-metal bond. 5. Structure determination of heterodimetallic cyano complexes in aqueous solution by EXAFS and vibrational spectroscopy
Vise andre og tillknytning
2001 (engelsk)Inngår i: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 40, nr 16, s. 3889-3899Artikkel i tidsskrift (Fagfellevurdert) Published
Abstract [en]

The structures of three closely related heterodimetallic cyano complexes, [(NC)(5)Pt-Tl(CN)(n)](n-) (n = 1-3), formed in reactions between [Pt-II(CN)(4)](2-) and Tl-III cyano complexes, have been studied in aqueous solution. Multinuclear NMR data ((TI)-T-205, Pt-195, and C-13) were used for identification and quantitative analysis. X-ray absorption spectra were recorded at the Pt and TlLIII edges. The EXAFS data show, after developing a model describing the extensive multiple scattering within the linearly coordinated cyano ligands, short Pt-Tl bond distances in the [(NC)(5)Pt-Tl(CN)(n)](n-) complexes: 2.60(1), 2.62(1), and 2.64(1) Angstrom for n = 1-3, respectively. Thus, the Pt-Tl bond distance increases with increasing number of cyano ligands on the thallium atom. In all three complexes the thallium atom and five cyano ligands, with a mean Pt-C distance of 2.00-2.01 Angstrom, octahedrally coordinate the platinum atom. In the hydrated [(NC)(5)Pt-Tl(CN)(H2O)(4)](-) species the thallium atom coordinates one cyano ligand, probably as a linear Pt-TI-CN entity with a Tl-C bond distance of 2.13(1) Angstrom, and possibly four loosely bound water molecules with a mean Tl-O bond distance of about 2.51 Angstrom. In the [(NC)(5)Pt-Tl(CN)(2)](2-) species, the thallium atom probably coordinates the cyano ligands trigonally with two TI-C bond distances at 2.20(2) Angstrom, and in [(NC)(5)Pt-Tl(CN)(3)]Tl3- coordinates tetrahedrally with three TI-C distances at 2.22(2) Angstrom. EXAFS data were reevaluated for previously studied mononuclear thallium(III)-cyano complexes in aqueous solution, [Tl(CN)(2)(H2O)(4)](+), [Tl(CN)(3)(H2O)], and [Tl(CN)(4)](-), and also for the solid K[TI(CN)(4)] compound. A comparison shows that the TI-C bond distances are longer in the dinuclear complexes [(NC)(5)Pt-TI(CN)(n)](n-) (it = 1-3) for the same coordination number. Relative oxidation states of the metal atoms were estimated from their Pt-195 and (TI)-T-205 chemical shifts, confirming that the I(NC)5Pt-TI(CN),]n- complexes can be considered as metastable intermediates in a two-electron-transfer redox reaction from platinum(II) to thallium(III). Vibrational spectra were recorded and force constants from normal-coordinate analyses are used for discussing the delocalized bonding in these species.

sted, utgiver, år, opplag, sider
2001. Vol. 40, nr 16, s. 3889-3899
Emneord [en]
ray-absorption spectra, tl, constants, palladium, ions, nmr
Identifikatorer
URN: urn:nbn:se:kth:diva-20839DOI: 10.1021/ic010055hISI: 000170199100009OAI: oai:DiVA.org:kth-20839DiVA, id: diva2:339536
Merknad
QC 20100525Tilgjengelig fra: 2010-08-10 Laget: 2010-08-10 Sist oppdatert: 2017-12-12bibliografisk kontrollert

Open Access i DiVA

Fulltekst mangler i DiVA

Andre lenker

Forlagets fulltekst

Søk i DiVA

Av forfatter/redaktør
Glaser, Julius
Av organisasjonen
I samme tidsskrift
Inorganic Chemistry

Søk utenfor DiVA

GoogleGoogle Scholar

doi
urn-nbn

Altmetric

doi
urn-nbn
Totalt: 50 treff
RefereraExporteraLink to record
Permanent link

Direct link
Referera
Referensformat
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Annet format
Fler format
Språk
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Annet språk
Fler språk
Utmatningsformat
  • html
  • text
  • asciidoc
  • rtf