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Sökning: onr:"swepub:oai:DiVA.org:kth-20839" > New class of oligon...

  • Jalilehvand, F. (författare)

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

  • Artikel/kapitelEngelska2001

Förlag, utgivningsår, omfång ...

  • 2001-06-27
  • American Chemical Society (ACS),2001
  • printrdacarrier

Nummerbeteckningar

  • LIBRIS-ID:oai:DiVA.org:kth-20839
  • https://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-20839URI
  • https://doi.org/10.1021/ic010055hDOI
  • https://urn.kb.se/resolve?urn=urn:nbn:se:umu:diva-8989URI

Kompletterande språkuppgifter

  • Språk:engelska
  • Sammanfattning på:engelska

Ingår i deldatabas

Klassifikation

  • Ämneskategori:ref swepub-contenttype
  • Ämneskategori:art swepub-publicationtype

Anmärkningar

  • QC 20100525
  • 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.

Ämnesord och genrebeteckningar

  • ray-absorption spectra
  • tl
  • constants
  • palladium
  • ions
  • nmr

Biuppslag (personer, institutioner, konferenser, titlar ...)

  • Maliarik, M. (författare)
  • Sandstrom, M. (författare)
  • Mink, J. (författare)
  • Persson, I. (författare)
  • Persson, PerUmeå universitet,Kemiska institutionen(Swepub:umu)pepe0002 (författare)
  • Toth, I. (författare)
  • Glaser, JuliusKTH,Kemi(Swepub:kth)u13oy1f4 (författare)
  • Umeå universitetKemiska institutionen (creator_code:org_t)

Sammanhörande titlar

  • Ingår i:Inorganic Chemistry: American Chemical Society (ACS)40:16, s. 3889-38990020-16691520-510X

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