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Sökning: id:"swepub:oai:DiVA.org:kth-20657" > Tl-Pt(CN)(5) in the...

LIBRIS Formathandbok  (Information om MARC21)
FältnamnIndikatorerMetadata
00004205naa a2200529 4500
001oai:DiVA.org:kth-20657
003SwePub
008100810s2001 | |||||||||||000 ||eng|
024a https://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-206572 URI
024a https://doi.org/10.1002/1521-3765(20010518)7:10<2167::AID-CHEM2167>3.0.CO;2-M2 DOI
040 a (SwePub)kth
041 a engb eng
042 9 SwePub
072 7a ref2 swepub-contenttype
072 7a art2 swepub-publicationtype
100a Jalilehvand, F.4 aut
2451 0a Tl-Pt(CN)(5) in the solid state - A multimethod study of an unusual compound containing inorganic wires
264 1c 2001
338 a print2 rdacarrier
500 a QC 20100525
520 a The crystal and molecular structure of a polycrystalline powder with a metal-metal bond and the composition TlPt(CN)(5) has been determined by combining results from X-ray powder diffraction (XRD), extended X-ray absorption fine structure (EXAFS) and vibrational spectroscopic studies. The XRD data gave the tetragonal space group P4/nmm (No. 129). with a = 7.647(3), c = 8.049(3) Angstrom, Z = 2, and well-determined positions of the heavy metal atoms. The Pt-Tl bond length in the compound is 2.627(2) Angstrom. The platinum atom coordinates four equivalent equatorial cyano ligands, with a fifth axial CN ligand and a thallium atom completing a distorted octahedral coordination geometry. The Tl-Pt(CN)(5) entities are linked together in linear -NC-Pt-Tl-NC-Pt-Tl chains through the axial cyano ligand. These linear wires are the essential structural features and influence the properties of the com-pound. A three-dimensional network is formed by the four equatorial cyano ligands of the platinum atom that form bridges to the thallium atoms of neighbouring antiparallel chains. The platinum atom and the five nitrogen atoms from the bridging cyano groups form a distorted octahedron around the thallium atom. EXAFS data were recorded at the Pt and Tl L-III edges for a more complete description of the local structure around the Pt and Tl atoms. The excessive multiple scattering was evaluated by means of the FEFF program. Raman and infrared absorption spectroscopy reveal strong coupling of the vibrational modes of the TlPt(CN)(5) entities, in particular the metal - metal stretching mode, which is split into four Raman and two IR bands. Factor group theory shows that a structural unit larger than the crystallographic unit cell must be used to assign vibrational bands. Intra- and intermolecular force constants have also been calculated. The compound exhibits red luminescence at 700+/- 3 nm in glycerol and has a corresponding excitation maximum at 240 nm. X-ray photoelectron spectra (XPS) show that the metal atoms have intermediate oxidation states, Pt3.2+ and Tl1.6+, between those in the parent Pt-II and Tl-III species and the decomposition products, Pt-IV and Tl-I. The solid compound TlPt(CN)(5) is stable to 520 degreesC. However in presence of water, a two-electron transfer between the metal atoms results in the cleavage of the metal-metal bond at 80 degreesC, forming a Pt-IV pentacyanohydrate complex and a monovalent thallium ion.
653 a cyanides
653 a EXAFS spectroscopy
653 a platinum
653 a thallium
653 a X-ray diffraction
653 a platinum-thallium compounds
653 a metal-metal bond
653 a aqueous-solution
653 a structural characterization
653 a absorption-spectra
653 a complexes
653 a tl2pt(cn)4
653 a palladium
653 a pt(cn)42
653 a ions
700a Eriksson, L.4 aut
700a Glaser, Juliusu KTH,Kemi4 aut0 (Swepub:kth)u13oy1f4
700a Maliarik, M.4 aut
700a Mink, J.4 aut
700a Sandstrom, M.4 aut
700a Toth, I.4 aut
700a Toth, J.4 aut
710a KTHb Kemi4 org
773t Chemistry - A European Journalg 7:10, s. 2167-2177q 7:10<2167-2177x 0947-6539x 1521-3765
8564 8u https://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-20657
8564 8u https://doi.org/10.1002/1521-3765(20010518)7:10<2167::AID-CHEM2167>3.0.CO;2-M

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