Controlled Synthesis of Pnicogen–Chalcogen Polycations in Ionic Li­quids. Issue 6 (22nd January 2016)

• Record Type: Journal Article
• Authors: Groh, Matthias F.; Isaeva, Anna; Müller, Ulrike; Gebauer, Paul; Knies, Maximilian; Ruck, Michael
• Is Part Of: European journal of inorganic chemistry. Issue 6(2016)
• Page Start: 880
• Page End: 889
• Publication Date: 2016-01-22
• Subjects: Chalcogens -- Heterocubanes -- Ionic liquids -- Pnicogens -- Polycations; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201501430
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: Three new pnicogen–chalcogen polycations were synthesized under specific conditions in the Lewis‐acidic ionic liquids (ILs) [EMIm] X · n Al X 3 and [BMIm] X · n Al X 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 [Bi6 Te4 Br2 ] 4+ in triclinic [Bi6 Te4 Br2 ](AlBr4 )4 as the reaction product of bismuth, tellurium, and bismuth tribromide. Substitution of the elements with Bi2 Te3 yielded the heterocubane [Bi4 Te4 ] 4+ in tetragonal [Bi4 Te4 ](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. Bi2 S3, which is insoluble in most media, readily dissolves in the employed IL and forms the new augmented heterocubane [Bi3 S4 AlCl] 3+, which crystallizes with the complex anion [S(AlCl3 )3 ] 2– as triclinic [Bi3 S4 AlCl][S(AlCl3 )3 ]AlCl4 . Quantum‐chemical calculations support the assignment of elements in this compound. The monoclinic crystal structure of [Sb13 Se16 ](AlCl4 )6 (Al2 Cl7 ) contains a new member of the small family of pnicogen–chalcogen spiro ‐heterocubanes. Abstract : Heteropolycations: Three new pnicogen–chalcogen polycations were synthesized in imidazolium‐based Lewis‐acidic ionic liquids (IL) at moderate temperatures. Bi2 S3, usually soluble only under harsh conditions, readily dissolves and reacts in the employed IL to give a quaternary polycation. The choice of starting materials and the reaction temperature were identified as important control parameters.