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Journal Article

Controlled Synthesis of Pnicogen-Chalcogen Polycations in Ionic Liquids

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Ruck,  Michael
Michael Ruck, Max Planck Fellow, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Citation

Groh, M. F., Isaeva, A., Mueller, U., Gebauer, P., Knies, M., & Ruck, M. (2016). Controlled Synthesis of Pnicogen-Chalcogen Polycations in Ionic Liquids. European Journal of Inorganic Chemistry, (6), 880-889. doi:10.1002/ejic.201501430.


Cite as: https://hdl.handle.net/11858/00-001M-0000-002A-30F6-5
Abstract
Three new pnicogen-chalcogen polycations were synthesized under specific conditions in the Lewis-acidic ionic liquids (ILs) [EMIm]XnAlX(3) and [BMIm]XnAlX(3) (X = Cl, Br; [EMIm]: 1-ethyl-3-methylimidazolium, [BMIm]: 1-butyl-3-methylimidazolium) and crystallized as their tetrahalogenidoaluminate salts. Single-crystal X-ray diffraction revealed the new polycation [Bi6Te4Br2](4+) in triclinic [Bi6Te4Br2](AlBr4)(4) as the reaction product of bismuth, tellurium, and bismuth tribromide. Substitution of the elements with Bi2Te3 yielded the heterocubane [Bi4Te4](4+) in tetragonal [Bi4Te4](AlBr4)(4), which crystallizes isotypically to its known chlorine counterpart. The latter is also accessible from ILs. The interactions between cations and anions were evaluated by quantum-chemical calculations. Bi2S3, which is insoluble in most media, readily dissolves in the employed IL and forms the new augmented heterocubane [Bi3S4AlCl](3+), which crystallizes with the complex anion [S(AlCl3)(3)](2-) as triclinic [Bi3S4AlCl][S(AlCl3)(3)]AlCl4. Quantum-chemical calculations support the assignment of elements in this compound. The monoclinic crystal structure of [Sb13Se16](AlCl4)(6)(Al2Cl7) contains a new member of the small family of pnicogen-chalcogen spiro-heterocubanes.