Synthesis of Organic (Trimethylsilyl)chalcogenolate Salts Cat[TMS-E] (E = S, Se, Te): the Methylcarbonate Anion as a Desilylating Agent

A high-yield synthesis of the class of (trimethylsilyl)­chalcogenolate organic salts [Cat]­[TMS-E] (E = S, Se, Te; Cat = BMPyr, DMPyr, NMe₄, <i>n</i>Bu₃MeP) is presented. The title compounds have been prepared by the strictly aprotic reaction between the respective bis­(trimethylsilyl)­chalcogenide (TMS₂E) and methylcarbonate ionic liquids (ILs). This constitutes a novel reaction behavior of methylcarbonate ILs, acting as a nucleophilic desilylating agent and a Lewis base instead of as a Brønsted base. Thus prepared silylchalcogenolate salts represent an activated form of the multifunctional TMS₂E reactant series. Pyrrolidinium TMS-S salts have proven to be excellent precursors for the synthesis of pyrrolidinium hexasulfides. The scope of the desilylation reaction can be extended to other silyl-bearing synthons such as (trimethylsilyl)­azide and (trimethylsilyl)­cyanide

The New NH-Acid HN(C₆F₅)(C(CF₃)₃) and Its Crystalline and Volatile Alkaline and Earth Alkaline Metal Salts

Herein we report on the new NH-acid <i>N</i>-(2,3,4,5,6-pentafluorophenyl)-<i>N</i>-nonafluoro-<i>tert</i>-butylamine, HN­(C₆F₅)­(C­(CF₃)₃), bearing two different sterically demanding and strongly electron-withdrawing perfluorinated amine substituents. The title compound and seven of its alkaline and alkaline earth metal salts were synthesized and investigated concerning their thermal, spectroscopic, and structural properties. The Li, Na, K, Cs, and Mg salts were investigated by single-crystal XRD analysis. The molecular structures reveal interesting motifs such as manifold fluorine metal secondary interactions. The lithium and magnesium compounds exhibit a remarkable thermal stability and an unexpectedly high volatility. We believe that this report will provoke investigations to apply the corresponding anion in ionic liquids, in lithium electrolytes, and as a weakly electron-donating ligand in the preparation of highly Lewis-acidic main group, rare earth, or transition metal complexes

Mercurates from a Revised Ionothermal Synthesis Route: The <i>Pseudo</i>-Flux Approach

K₂Hg₆Se₇, Na₂Hg₃S_2.51Se_1.49, K₂Hg₃S_1.03Se_2.97, and K₂Hg₃S_2.69Se_1.31 were prepared by ionothermal treatment of K₂Hg₂Se₃, Na₂HgSe₂, and K₂Hg₃Se₄, respectively, in a nonclassical hydrosulfide ionic liquid (EMIm)­(SH). In contrast to their lighter congeners, the title compounds could so far not be synthesized by inorganic polychalcogenide salt flux techniques. The applied method hence mimics polychalcogenide flux conditions, while operating at much lower temperatures below the decomposition temperature of the ionic liquid. It might thus be viewed as a <i>pseudo</i>-flux approach