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Simplified Synthesis and Structural Study of { Ta6Br12} Clusters
Authors:Maxim N Sokolov  Pavel A Abramov  Maxim A Mikhailov  Eugenia V Peresypkina  Alexander V Virovets  Vladimir P Fedin
Institution:1. A. 2. V. Nikolaev Institute of Inorganic Chemistry, Russian Academy of Sciences, Lavrentiev Avenue 3, Novosibirsk, 630090, Russia;3. Novosibirsk State University, ul. Pirogova 3,Novosibirsk, 630090, Russia
Abstract:Direct reaction of stoichiometric amounts of KBr, tantalum and bromine at 720 °C, followed by extraction and crystallization gives Ta6Br14 · 7H2O (1) . This compound slowly aquates into (Ta6Br12)(H2O)6]2+, which crystallized as mixed Cs+/Br ( 2 ), Cl ( 3 ) and SO42– ( 4 ) salts. In Bu4NBr melt, 1 undergoes oxidation into (Bu4N)2(Ta6Br12)Br6] ( 5 ). Reaction of 1 with dimethylsulfoxide also induces oxidation of the { Ta6Br12} 2+ core into { Ta6Br12} 4+, and the corresponding complex (Ta6Br12)(dmso)2Cl4] · iPrOH · 4.8H2O ( 6 ) was isolated and structurally characterized. Molecular and crystal structures for 2 – 6 were determined.
Keywords:Cluster compounds  Tantalum  Bromine  X‐ray diffraction  IR spectroscopy
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