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Electrochemical synthesis, structural characterization, and decomposition of rhenium oxoethoxide, Re4O4(OEt)12. Ligand influence on the structure and bonding in the high-valent tetranuclear planar rhenium alkoxide clusters

Nikonova, Olesya A ; Jansson, Kjell ; Kessler, Vadim G ; Sundberg, Margareta ; Baranov, Alexei I ; Shevelkov, Andrei V ; Drobot, Dmitrii V ; Seisenbaeva, Gulaim A

Inorganic chemistry, 18 February 2008, Vol.47(4), pp.1295-300 [Periódico revisado por pares]

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  • Título:
    Electrochemical synthesis, structural characterization, and decomposition of rhenium oxoethoxide, Re4O4(OEt)12. Ligand influence on the structure and bonding in the high-valent tetranuclear planar rhenium alkoxide clusters
  • Autor: Nikonova, Olesya A ; Jansson, Kjell ; Kessler, Vadim G ; Sundberg, Margareta ; Baranov, Alexei I ; Shevelkov, Andrei V ; Drobot, Dmitrii V ; Seisenbaeva, Gulaim A
  • Assuntos: Inorganic Chemistry ; Oorganisk Kemi
  • É parte de: Inorganic chemistry, 18 February 2008, Vol.47(4), pp.1295-300
  • Descrição: Anodic oxidation of rhenium in ethanol in the presence of LiCl as a conductive additive results with high yield in formation of a new oxoethoxide cluster, Re(4)O(4)(OEt)(12). The structure of the planar centrosymmetric metal-oxygen core of this molecule is composed of four edge-sharing Re(V)O(6) octahedra. Eight electrons are available for the formation of metal-metal bonds indicated by five relatively short Re-Re distances within the Re 4-rhombus, a "planar butterfly" type cluster. The theoretical calculations are indicating relatively low contribution of metal-metal bonding in the stability of the core. The stability of the +V-oxidation state, unusual for rhenium alkoxides can be at least partially attributed to the size effects in the packing of ligands. The X-ray powder study indicates that treatment of Re(4)O(4)(OEt)(12). in ambient atmosphere rapidly transforms it into a mixed-valence derivative Re(4)O(6)(OEt)(10) with a structure related to the earlier investigated cluster Re(4)O(6)(O(i)Pr)(10)....
  • Idioma: Inglês

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