Current advances in tin cluster chemistry

Abstract

Clusters containing tin atoms show a huge variety of molecular structures, chemical as well as physical properties.

Towards Understanding the Reactivity and Optical Properties of Organosilicon Sulfide Clusters

“…In particular, a large variety of compounds has been reported for the element combinations Sn/E [1a, 2] (E=S, Se, Te) and Ge/E, [1c, 3] whereas significantly fewer compounds with Si/E‐based cluster cores have been known so far [1b, 4] . Several studies investigating the reactivity and properties of tin chalcogenide clusters were undertaken, showing the possible derivatization of the organic substituents [5, 2f] as well as the formation of ternary inorganic cluster cores by introducing transition metal complexes [6]…”

Structural Expansion of Chalcogenido Tetrelates in Ionic Liquids by Incorporation of Sulfido Antimonate Units

“…Besides comparably established syntheses under solvothermal reaction conditions [16–20] or in alkali metal polychalcogenide flux, [21] reactions in ionic liquids have become a very popular method in more recent times for the transformation of chalcogenido (semi)metalates. The products are usually obtained as single‐crystalline material, which allows the subsequent investigation of their structural as well as concomitant physical properties [20, 22–29] …”

“…The products are usually obtained as single-crystalline material, which allows the subsequent investigation of their structurala sw ell as concomitant physicalproperties. [20,[22][23][24][25][26][27][28][29] In our work, we have been particularly interested in the formationa nd transformation of chalcogenido tetrelate anions [Tt x E y ] qÀ (Tt = Ge, Sn), therebya ddressing changes of structures and physical properties in athreefold manner,bya)dimensional changes within binaryn etworks, [25,[30][31][32][33][34] b) combination of two types of tetrel atoms, [35,36] and c) admixtureo ft ransition metal atoms. [34,37] In all three cases, the whole reaction spaceincluding the nature of the ionic liquid, the used precursors, potentiala uxiliary compounds, reactiont emperature and time-needs to be scanned to getasufficiently deep insight into the corresponding reaction system.A saside effect, we could recently showt hat alkylimidazolium-basedi onic liquids (C l C m C n Im) [An]( C l ,C m ,C n = alkyl groups with l, m, or nCa toms in 1, 2, or 3p osition of the imidazolium (Im) ring;[ An] = Cl, Br, [BF 4 ]) can serve as mild and relatively benign alkylation reagentsf or these weakly nucleophilic chalcogenido (semi)metalate compounds, which has also been the only way of achieving their post-synthetic alkylation to date.…”

Highly Soluble Supertetrahedra upon Selective Partial Butylation of Chalcogenido Metalate Clusters in Ionic Liquids

“…Recently,wereported first promising results by presenting am ethod that allowed to form salts of partially methylated chalcogenido metalate clusters,w hich were heretofore only known as purely inorganic and highly charged molecules. [16,17] Themethylation was achieved by ionothermal syntheses [18] in imidazolium-based ionic liquids (C l C m C n Im)X (C l ,C m ,C n = alkyl chains with l, m,orn carbon atoms in 1-, 2-, or 3-position of the imidazolium ring Im;X= Cl, Br,[ BF 4 ]). [19] With l or n being 1, thus ionic liquids with methyl substituents at one of the nitrogen atoms,t he methyl group was selectively transferred to the terminal chalcogenide ligands of the investigated clusters,w hich served to reduce the negative charge of the anion by the number of alkyl substituents-for instance from À8i n[ Sn 10 O 4 S 20 ] 8À [20][21][22] to À4i n[ Sn 10 O 4 S 16 (SMe) 4 ] 4À .…”

“…Recently, we reported first promising results by presenting a method that allowed to form salts of partially methylated chalcogenido metalate clusters, which were heretofore only known as purely inorganic and highly charged molecules [16, 17] . The methylation was achieved by ionothermal syntheses [18] in imidazolium‐based ionic liquids (C l C m C n Im)X (C l , C m , C n =alkyl chains with l , m , or n carbon atoms in 1‐, 2‐, or 3‐position of the imidazolium ring Im; X=Cl, Br, [BF 4 ]) [19] .…”