Room-Temperature Synthesis of the Bi 5 [GaCl 4 ] 3 Salt From Three Different Classes of Ionic Liquids
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Room-Temperature Synthesis of the Bi5[GaCl4]3 Salt From Three Different Classes of Ionic Liquids ˚ kerstedt • Mikhail Gorlov • Lars Kloo Josefin A
Received: 27 September 2012 / Published online: 2 December 2012 Ó Springer Science+Business Media New York 2012
Abstract Following the development in the synthesis of subvalent cluster compounds, we report on the use of three different classes of room-temperature ionic liquids for the synthesis of the pentabismuth-tris(tetragallate) salt, Bi5[GaCl4]3, characterized by X-ray diffraction. The Bi5[GaCl4]3 salt was prepared by reduction of BiCl3 using gallium metal in ionic liquid reaction media containing a strong Lewis acid, GaCl3. The ionic liquids; trihexyltetradecyl phosphonium chloride [Th-Td-P?]Cl-, 1-dodecyl-3-methylimidazolium chloride [Dod-Me-Im?]Cl- and N-butyl-N-methylpyrrolidinium chloride [Bu-Me-Pyrr?]Cl- from three of the main classes of ionic liquids were used in synthesis. Reactions using ionic liquids composed of the trihexyltetradecyl phosphonium cation [Th-Td-P?] and the anions; tetrafluoroborate [BF4-], bis(trifluoro-methyl sulfonyl) imide [(Tf)2N-] and hexafluorophosphate [PF6-] were also investigated. Keywords Bismuth Polycation Cluster compounds Ionic liquids X-ray diffraction
Introduction Subvalent cluster species are known to communicate unexpected chemical bonding and properties, due to their unusually reduced oxidation state. This leads to a unique structural chemistry [1]. The heavier p-block elements, amongst them bismuth, tend to form subvalent species in the form of homonuclear polycationic clusters [2]. Electronic supplementary material The online version of this article (doi:10.1007/s10876-012-0526-3) contains supplementary material, which is available to authorized users. ˚ kerstedt M. Gorlov L. Kloo (&) J. A Applied Physical Chemistry, KTH Royal Institute of Technology, Teknikringen 30, SE-100 44 Stockholm, Sweden e-mail: [email protected]
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Some examples of homonuclear bismuth clusters reported are: Bi5? [3, 4], Bi62? [3–5], Bi82? [6–8], Bi95? [9–19], Bi104? [20–24], (the latter stabilized by capping or enclosed heteroatoms) and the pentabismuth polycation; Bi53? [12, 25–27], all of which have been obtained from a range of synthetic routes. Referring to the solid phases isolated the Bi53? and Bi95? must be regarded as the most common examples. However, it is not obvious for what reason it may either be intrinsic electronic or selection of counter ions that influence this preference [28, 29]. Bismuth is one of the most studied cluster-forming elements of the main group, and subvalent bismuth species have been shown to demonstrate peculiar physiochemical properties. Subvalent cluster species such as the Bi82? and Bi53? have for instance been shown to be photoluminescent in the near-infrared region [30]. During the last 40 years the synthetic routes to subvalent clusters in general and homonuclear bismuth polycations in particular have undergone significant development. The initial molten salt method
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