Synthesis and structure of monomeric and platinum-bonded (1,10-phenanthroline)thallium complexes
2002 (English)In: European Journal of Inorganic Chemistry, ISSN 1434-1948, E-ISSN 1099-0682, no 6, 1307-1314 p.Article in journal (Refereed) Published
Oxidative addition of (1,10-phenanthroline)thallium(III) complexes [TI(phen)(n)(solv)](3+) (n = 1-2) (phen = 1,10-phenanthroline) to [Pt(CN)(4)](2-) in DMSO, in the presence of cyanide ions and in the absence of cyanide ions yielded heterodinuclear metal-metal-bonded complexes, [(NC)(5)Pt-Tl(phen)(n)(solv)] and [(NC)(4)Pt-Tl(phen)(n)(solv)](+) (n = 0, 1, and 2), respectively, The presence of a direct Pt-Tl bond in the complex is evident by a very strong one-bond Pt-195-Tl-205 spin-spin coupling detected by Tl-205 NMR: (1)J = 94.0 kHz (1a), 84.2 kHz (2a), and 77.1 kHz (3a) corresponding to n 0, 1, and 2 in [(NC)(4)Pt-Tl(phen)(n)(solv)](+), and (1)J 65.4 kHz (2b) and 62.5 kHz (3b) for n = 1 and 2, respectively, in [(NC)(5)Pt-Tl(phen)(n)(solv)]. The crystal structures of [(NC)(5)Pt-Tl(phen)(DMSO)(3)].(DMSO) (2b), [(NC)(5)Pt-Tl(phen)(2)].(DMSO)(3) (3b), and [Tl(phen)(2)Cl-2] (ClO4) (4) complexes were determined. Very short Pt-Tl bonds, 2.6296(3) and 2.6375(5) Angstrom, are present in structures 2b and 3b, respectively. The corresponding force constants in the molecules in the solid state, 1.84 and 1.74 N/cm for 2b and 3b, respectively, were calculated using Raman stretching frequencies of the Pt-Tl vibrations, and are characteristic for a single, strong metal-metal bond. Electronic absorption spectra were recorded for selected compounds and the optical transition attributed to the metal-metal bond was assigned. ((C) Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002).
Place, publisher, year, edition, pages
2002. no 6, 1307-1314 p.
metal-metal interactions, platinum, thallium, N ligands, NMR spectroscopy, metal-metal bond, x-ray structures, aqueous-solution, thallium compounds, solid-state, <(nc)(5)pt-tl(cn)>(-), mercury(0), chloride, clusters, crystal
IdentifiersURN: urn:nbn:se:kth:diva-21594ISI: 000175988500007OAI: oai:DiVA.org:kth-21594DiVA: diva2:340292
QC 201005252010-08-102010-08-10Bibliographically approved