Tunable aryl alkyl ionic liquids (TAAILs) are a promising class of imidazolium-or triazolium-based ionic liquids. Contrary to "standard" all-alkyl ionic liquids, these carry an aryl ring together with a linear or branched alkyl chain. Their application in the cobalt-catalyzed hydroarylation/hydroamination of alkenes and anilines is presented. The catalytic system is tolerant toward air and is scalable and reusable. It has been successfully used for the synthesis of pharmacologically relevant primary to tertiary aryl amines.

Weakly coordinating borate or aluminate anions have recently been shown to yield interesting properties of the resulting ionic liquids (ILs). The same is true for large phenyl-substituted imidazolium cations, which can be tuned by the choice, position, or number of substituents on the aromatic ring. We were therefore interested to combine these aryl alkyl imidazolium cations with the weakly coordinating tetrakis((1,1,1,3,3,3-hexafluoropropan-2-yl)oxy)borate [B(hfip)4 ](-) anions to study the physical properties and viscosities of these ionic liquids. Despite the large size and high molecular weight of these readily available ILs, they are liquid at room temperature and show remarkably low glass transition points and relatively high decomposition temperatures.

Vaporization enthalpies of five different imidazolium based Tunable Aryl Alkyl Ionic Liquids (TAAILs) with a common bis(trifluoromethylsulfonyl)imide ([NTf2]) anion were measured using a Quartz Crystalline Microbalance (QCM) and by Thermogravimetric Analysis (TGA). The counter anion and the alkyl chain of these imidazolium‐based ionic liquids with one N‐aryl and one N‐alkyl substituent were kept constant to study the influence of the ortho‐ and para‐substituted aryl moieties on the vaporization enthalpies of these ionic liquids. For comparison, enthalpies of vaporization measured at elevated temperatures were adjusted to the reference temperature 298 K. Structure‐property relations between TAAILs and similarly shaped corresponding 1‐(R‐phenyl)‐imidazoles were analyzed. An incremental approach to predict vaporization enthalpies of ionic liquids by group contributions was suggested. The procedure is based on vaporization enthalpy of a starting IL and group contributions well established from molecular compounds.

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Diimidazolium salts featuring different bridges between the imidazolium groups, as well as electron-withdrawing groups (chloride, cyanide) at the 4- and 5-position of the heterocyclic rings, have been successfully prepared. The diimidazolium salts serve as convenient precursors of di(N-heterocyclic carbene) ligands, which coordinate in a chelating fashion to palladium(ii) centres. The effect of the newly introduced electron-withdrawing groups on the spectroscopic and structural characteristics of the resulting complexes as well as on their reactivity as catalysts in a model alkyne hydroarylation reaction has been investigated and is discussed herein.