New Low-Melting Triply Charged Homoleptic Cr(III)-Based Ionic Liquids in Comparison to Their Singly Charged Heteroleptic Analogues

A series of new low-melting triply charged homoleptic Cr(III)-based ionic liquids of the general formula (RMIm)(3)[Cr(NCS)(6)] (R = methyl, ethyl, n-butyl, benzyl) is reported. Their syntheses and properties are described in comparison to their singly charged heteroleptic analogues of the general formula (RMIm)[Cr(NCS)(4)L(2)] (R = methyl, ethyl, n-butyl, benzyl; L = pyridine, γ-picoline). In total, sixteen new Reineckate related salts with large imidazolium cations are described. Out of these, five compounds were crystallized, and their structures determined by single-crystal X-ray structure analyses. They all consisted of discrete anions and cations with octahedrally coordinated Cr(III) ions. In the structures, various hydrogen contacts interconnect the entities to build up hydrogen bonded networks. Thermal investigations showed relatively low melting points for the homoleptic complexes. The compounds with the [Cr(NCS)(6)](3−) anion melt without decomposition and are stable up to 200 K above their melting points. The complex salts with the [Cr(NCS)(4)L(2)](−) anion, in contrast, start to decompose and lose L molecules (Pyr or Pic) already at the melting point.