Chalcogenido‐Dimethylgallates and ‐Indates DMPyr2[Me2M(μ2−E)]2 (M=Ga, In; E=S, Se): Building Blocks for Higher and Lower Order Chalcogenidoindates

ChemistryOpen

Dr. Klaus Harms¹  Prof. Dr. Jörg Sundermeyer¹  Tobias Vollgraff¹  Dr. Lars H. Finger¹  Dr. Jannick Guschlbauer¹ 

[1] Fachbereich Chemie and Materials Science Center Philipps-Universität Hans-Meerwein-Str. 4 35032 Marburg Germany;

关键词: Ionic liquids;    chalcogenido metalates;    chalcogenide materials;    gallium;    indium;   

DOI  :  10.1002/open.202000347

来源: DOAJ

【 摘 要 】

Abstract Metalation of the anions in the ionic liquids DMPyr[SH] and DMPyr[SeH] (DMPyr=1,1‐dimethylpyrrolidinium) by trimethylgallium and trimethylindium is investigated. The reaction proceeds via pre‐coordination of [EH]−, methane elimination and formation of an unprecedented series of chalcogenido metalates DMPyr2[Me2M(μ2−E)]2 (M=Ga, In; E=S, Se). These show the presences of dinuclear dianions with four‐membered ring structures displaying highly nucleophilic bridging chalcogenide ligands in their crystallographically determined molecular structures. Some representative reactions of these building blocks with amphoteric electrophiles were studied: Addition of two equivalents of E(SiMe3)2 (E=S, Se) to the indates DMPyr2[Me2In(μ2−S)]2 and DMPyr2[Me2In(μ2−Se)]2 leads to a cleavage of the ring, E silylation and formation of mononuclear, monoanionic indates DMPyr[Me2In(SSiMe3)2], DMPyr[Me2In(SeSiMe3)2], and even a mixed sulfido‐selenido dimethylindate DMPyr[Me2In(SSiMe3)(SeSiMe3)]. Reaction of DMPyr2[Me2In(μ2−S)]2 with two equivalents of Lewis acid Me3In leads to charge delocalization, ring expansion and formation of six‐membered ring DMPyr3[Me2In(μ2−S−InMe3)]3. The latter is a key intermediate in the formation of dianionic sulfidoindate DMPyr2[(Me2In)6(μ3−S)4] displaying an unusual inverse heteroadamantane cage structure with four capping sulfido ligands.

【 授权许可】

Unknown