A Methylated Oxo‐Thio Stannate Cluster from a Non‐Innocent Ionic Liquid

Abstract

A new salt of the alkylated oxo‐thio stannate cluster [Sn10O4S16(SMe)4]4–, (C4C4C1Im)4[Sn10O4S16(SMe)4] (1), was obtained by ionothermal treatment of K4[SnS4]·4H2O. The reaction was carried out in the ionic liquid 1,3‐dibutyl‐2‐methylimidazolium chloride, (C4C4C1Im)Cl, which proved to be non‐innocent against the chalcogenido metallate species in the reaction mixture. In continuation of our first studies on alkylation of very weakly nucleophilic chalcogenido metalate anions, this study served to prove that an N‐bonded alkyl group is selectively released from the imidazolium cation of the ionic liquid, and it served to show that methylation is favored over butylation. The title compound is one of the rare cases, in which the cations of the salt, which stem from the ionic liquid, could be crystallographically determined without problems.

Discrete Supertetrahedral Tn Chalcogenido Clusters Synthesized in Ionic Liquids: Crystal Structures and Photocatalytic Activity

“…Recently, they reported an isostructural one with [Bbmim] + cations as counterions (T3-12). [50] Because the methyl and butyl groups were suited in different sites in [Bmmim] + and [Bbmim] + , the selective transfer of N-bonded alkyl group and the favor of methylation to bind with terminal S atoms over butylation were confirmed. Different packing diagrams were dominated by different reacting conditions which resulted in different space groups, as shown in Table 1…”

“…[45-48,51À 52] Besides, [Bbmim]Cl (Figure 2, right; Bbmim = 1,2-dibutyl-3-methylimidazolium) and mixed ILs of [Bmmim]Cl/ [Bmmim][BF 4 ] were also utilized as the media for preparing methylated T3 clusters. [49][50] Thus far, there were four synthetic routes towards the preparation of discrete Tn chalcogenido clusters in ILs: (1) reaction between elements in ILs in the presence of auxiliary solvents; [46] (2) reacting simple metal salts or solid precursors such as…”

“…A = Li, Na or K, x = 4, 13 or 14) in ILs with or without other chalcogen source and auxiliary solvents; [45,47,[49][50] (3) preparing monometallic gel-like precursors such as InÀ QÀ ILs (Q = chalcogen elements) precursor in ILs and then reacting it with another metal salt in molecular solvents; [48,[51][52] (4) preparing bimetallic gel-like precursors such as CuÀ InÀ SeÀ IL precursor in ILs and crystallization (with chalcogen source) in auxiliary solvents. [52] In abovementioned routes, the microwave-assisted method had been widely adopted to obtain the gel-like precursors that were essential to obtain desired Tn clusters in some reactions.…”

“…Discrete supertetrahedral Tn (n > 3) clusters are normally charge-and space-compensated by the following types of cations: (1) alkali metal cations; [40] (2) protonated amines or ammoniums; [41][42] (3) protonated nitrogen heterocycle molecules; [43] (4) transition metal complexes; [44] and (5) cations of ionic liquids (ILs). [45][46][47][48][49][50][51][52] Since the first crystallization of discrete supertetrahedral T5 chalcogenido cluster from ILs, [45] 32 of Tn clusters have been obtained in ILs. [46][47][48][49][50][51][52] This minireview summarizes the syntheses, crystal structures and selected properties of discrete Tn chalcogenido clusters obtained in ILs.…”

“…[45][46][47][48][49][50][51][52] Since the first crystallization of discrete supertetrahedral T5 chalcogenido cluster from ILs, [45] 32 of Tn clusters have been obtained in ILs. [46][47][48][49][50][51][52] This minireview summarizes the syntheses, crystal structures and selected properties of discrete Tn chalcogenido clusters obtained in ILs. Especially, the photocatalytic activity enhancement by monodispersing discrete Tn chalcogenido clusters in solvents is highlighted.…”