Linked Life Data

11466046

Source:http://linkedlifedata.com/resource/pubmed/id/11466046

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PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
16
pubmed:dateCreated
2001-7-23
pubmed:abstractText
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 ((205)Tl, (195)Pt, and (13)C) were used for identification and quantitative analysis. X-ray absorption spectra were recorded at the Pt and Tl L(III) 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) A 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 A, octahedrally coordinate the platinum atom. In the hydrated [(NC)(5)Pt-Tl(CN)(H(2)O)(4)](-) species the thallium atom coordinates one cyano ligand, probably as a linear Pt-Tl-CN entity with a Tl-C bond distance of 2.13(1) A, and possibly four loosely bound water molecules with a mean Tl-O bond distance of about 2.51 A. In the [(NC)(5)Pt-Tl(CN)(2)](2)(-) species, the thallium atom probably coordinates the cyano ligands trigonally with two Tl-C bond distances at 2.20(2) A, and in [(NC)(5)Pt-Tl(CN)(3)](3)(-) Tl coordinates tetrahedrally with three Tl-C distances at 2.22(2) A. EXAFS data were reevaluated for previously studied mononuclear thallium(III)-cyano complexes in aqueous solution, [Tl(CN)(2)(H(2)O)(4)](+), [Tl(CN)(3)(H(2)O)], and [Tl(CN)(4)](-), and also for the solid K[Tl(CN)(4)] compound. A comparison shows that the Tl-C bond distances are longer in the dinuclear complexes [(NC)(5)Pt-Tl(CN)(n)()](n)()(-) (n = 1-3) for the same coordination number. Relative oxidation states of the metal atoms were estimated from their (195)Pt and (205)Tl chemical shifts, confirming that the [(NC)(5)Pt-Tl(CN)(n)()](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.
pubmed:language
eng
pubmed:journal
pubmed:citationSubset
IM
pubmed:chemical
pubmed:status
MEDLINE
pubmed:month
Jul
pubmed:issn
0020-1669
pubmed:author
pubmed:issnType
Print
pubmed:day
30
pubmed:volume
40
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
3889-99
pubmed:dateRevised
2008-11-21
pubmed:meshHeading
pubmed:year
2001
pubmed:articleTitle
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.
pubmed:affiliation
Department of Chemistry, Inorganic Chemistry, Royal Institute of Technology (KTH), SE-100 44 Stockholm, Sweden.
pubmed:publicationType
Journal Article, Research Support, U.S. Gov't, P.H.S., Research Support, U.S. Gov't, Non-P.H.S., Research Support, Non-U.S. Gov't