Ionic liquid cations as methylation agent for extremely weak chalcogenido metalate nucleophiles

Abstract

Imidazolium-based ionic liquids served to selectively methylate terminal chalcogenide ligands of chalcogenidometalate clusters [Sn10S16O4(SMe)4]4−, [Mn4Sn4Se13(SeMe)4]6−, and [Hg6Te10(TeMe)2]6−.

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

“…Characteristic bands of the S–C Me vibration can be found at 700 cm –1 , the signal of the C Me –H vibration is located around 1500 cm –1 (Figure a). As shown in Figure b, the signal groups between 150 and 400 cm –1 , which are assigned to the vibrations of the cluster core, match the cluster vibrations reported recently . Hence, the presence of (C 4 C 4 C 1 Im) + instead of (C 4 C 1 C 1 Im) + cations, i.e., the presence of another butyl group instead of a methyl group, does not affect the bonding within the supertetrahedral anions.…”

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

“…The signals observed at lower wavenumbers( up to 400 cm À1 )a re assigned to vibrations of the anionic substructures. These regionso ft he spectra of all three compounds reportedh erein, 1, 2a,a nd 2b,a nd the Raman spectrumo btained from the related compound (Cat) 4 [Sn 10 O 4 S 16 (SMe) 4 ], [37] are presented togetherinF igure 7.…”

“…[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. [37] As an ew meansoft uning the chalcogenido (semi)metalates' structurala nd electronic properties, we intendedt om ix two main group (semi)metal atoms of different main groups in cor-responding networks.…”

“…[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. [37] As an ew meansoft uning the chalcogenido (semi)metalates' structurala nd electronic properties, we intendedt om ix two main group (semi)metal atoms of different main groups in cor-responding networks. This was achieved by reactings alts of tetrahedral sulfido germanate or stannate anions, [38] with SbCl 3 in imidazolium-based ionic liquids (C 4 C 1 C 1 Im) [An].Instead of amere cation exchange, potentially along with ar eorganization of the anionic substructure (as observeda tt he formationo f1 D-(C 4 C 1 Im) 2 [Ge 4 Se 9 ] [33] or (Cat) 4 [Sn 10 O 4 S 16 (SMe) 4 ]w ith Cat = C 4 C 1 C 1 Im, [37] fori nstance, which form in the absence of other metal compounds), the pnictogen atoms were incorporated in the structures under ionothermal conditions.…”

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

“…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.…”