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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
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2008 (English)In: Inorganic Chemistry, Vol. 47, 1295-1300 p.Article in journal (Refereed) Published
Abstract [en]

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, Re4O4(OEt)12. The structure of the planar centrosymmetric metal–oxygen

core of this molecule is composed of four edge-sharing Re(V)O6 octahedra. Eight electrons are available for the

formation of metal-metal bonds indicated by five relatively short Re-Re distances within the Re4-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 Re4O4(OEt)12 in ambient atmosphere rapidly transforms it into a mixed-valence derivative

Re4O6(OEt)10swith a structure related to the earlier investigated cluster Re4O6(OiPr)10. Thermal decomposition of

the latter rhenium oxoethoxide results in reduction to rhenium metal at as low temperatures as 380 °C, producing

aggregates of metal nanoparticles with the average size of 3 nm.

Place, publisher, year, edition, pages
2008. Vol. 47, 1295-1300 p.
URN: urn:nbn:se:su:diva-15476ISI: 000253115300014OAI: diva2:181996
Available from: 2008-12-03 Created: 2008-12-03 Last updated: 2011-01-10Bibliographically approved

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