Friedel-Crafts acylation of benzene derivatives in tunable aryl alkyl ionic liquids (TAAILs).

An iron(III) chloride hexahydrate-catalyzed Friedel-Crafts acylation of benzene derivatives in tunable aryl alkyl ionic liquids (TAAILs) has been developed. Through optimization of the metal salt, reaction conditions and ionic liquids, we were able to design a robust catalyst system that tolerates different electron-rich substrates under ambient atmosphere and allows for a multigram scale.

Tunable Aryl Alkyl Ionic Liquid Supported Synthesis of Platinum Nanoparticles and Their Catalytic Activity in the Hydrogen Evolution Reaction and in Hydrosilylation.

Tunable aryl alkyl ionic liquids (TAAILs) are ionic liquids (ILs) with a 1-aryl-3-alkylimidazolium cation having differently substituted aryl groups. Herein, nine TAAILs with the bis(trifluoromethylsulfonyl)imide anion are utilized in combination with and without ethylene glycol (EG) as reaction media for the rapid microwave synthesis of platinum nanoparticles (Pt-NPs). TAAILs allow the synthesis of small NPs and are efficient solvents for microwave absorption. Transmission electron microscopy (TEM) shows that small primary NPs with sizes of 2 nm to 5 nm are obtained in TAAILs and EG/TAAIL mixtures. The Pt-NPs feature excellent activity as electrocatalysts in the hydrogen evolution reaction (HER) under acidic conditions, with an overpotential at a current density of 10 mA cm-2 as low as 32 mV vs the reversible hydrogen electrode (RHE), which is significantly lower than the standard Pt/C 20% with 42 mV. Pt-NPs obtained in TAAILs also achieved quantitative conversion in the hydrosilylation reaction of phenylacetylene with triethylsilane after just 5 min at 200 °C.

The Facile Deposition of Pt Nanoparticles on Reduced Graphite Oxide in Tunable Aryl Alkyl Ionic Liquids for ORR Catalysts.

In this study, we present the facile formation of platinum nanoparticles (Pt-NPs) on reduced graphite oxide (rGO) (Pt-NP@rGO) by microwave-induced heating of the organometallic precursor ((MeCp)PtMe3 in different tunable aryl alkyl ionic liquids (TAAIL). In the absence of rGO, transmission electron microscopy (TEM) reveals the formation of dense aggregates of Pt-NPs, with primary particle sizes of 2 to 6 nm. In contrast, in the Pt-NP@rGO samples, Pt-NPs are homogeneously distributed on the rGO, without any aggregation. Pt-NP@rGO samples are used as electrode materials for oxygen reduction reaction (ORR), which was assessed by cyclic voltammetry (CV) and linear sweep voltammetry (LSV). The electrochemical surface area (ECSA) and mass-specific activity (MA) increase up to twofold, compared with standard Pt/C 60%, making Pt-NP@rGO a competitive material for ORR.

Synthesis and Physical Properties of Tunable Aryl Alkyl Ionic Liquids (TAAILs).

Tunable aryl alkyl ionic liquids (TAAILs) based on the imidazolium cation were first reported in 2009. Since then, a series of TAAILs with different properties due to the electron-donating or -withdrawing effect of the substituents at the aryl ring has been developed. Herein, a wide variety of those ionic liquids (ILs) is presented in terms of their cation structure. The authors synthesized ILs containing the bromide or bis(trifluoromethane)sulfonimide anion and 1-aryl-3-alkyl imidazolium cations with various substituents in the ortho and/ or para position of the phenyl ring and alkyl chains of different lengths varying from butyl to dodecyl. The differences of their physical properties (melting point, thermal decomposition, viscosity, electro-chemical window) of these ILs are reported according to their structure.

Tetrakis(pentafluoroethyl)gallate, [Ga(C2 F5 )4 ]- , Ionic Liquids.

We synthesized new imidazolium-based tunable aryl alkyl ionic liquids (TAAILs) with the weakly coordinating tetrakis(pentafluoroethyl)gallate anion, [Ga(C2 F5 )4 ]- . Phenyl and phenyl derivatives (2-Me, 4-OMe, 2,4-F) were combined with varying alkyl chain lengths at the imidazolium core leading to TAAILs, which were investigated with regard to their viscosity, conductivity, and electrochemical window and compared to EMIM and BMIM standard cations. Remarkable low viscosities of 29 cP at 25 °C for [BMIM][Ga(C2 F5 )4 ] were achieved. However, the EMIM and BMIM gallates show electrochemical instability, releasing pentafluoroethane at a voltage of 1.5 V. The 2-Me-substituted gallate-TAAILs slowly decompose over several weeks, whereas all other gallate-TAAILs showed no decomposition at all. With electrochemical windows of up to 5.15 V and low viscosities in a range of 66-162 cP, the gallate-TAAILs are promising candidates as electrolytes in electrochemical applications.

Type-II Clathrate Na24-δ Ge136 from a Redox-Preparation Route.

The metastable type-II clathrate Na24-δ Ge136 was obtained from Na12 Ge17 by applying a two-step procedure. At first, Na12 Ge17 was reacted at 70 °C with a solution of benzophenone in the ionic liquid (IL) 1,3-dibutyl-2-methylimidazolium-bis(trifluoromethylsulfonyl) azanide. The IL was inert towards Na12 Ge17 , but capable of dissolving the sodium salts formed in the redox reaction. By annealing at 340 °C under an argon atmosphere, the X-ray amorphous intermediate product was transformed to crystalline Na24-δ Ge136 (δ≈2) and α-Ge in an about 1 : 1 mass ratio. The product was characterized by X-ray powder diffraction, chemical analysis, and 23 Na solid-state NMR spectroscopy. Metallic properties of Na24-δ Ge136 were revealed by a significant Knight shift of the 23 Na NMR signals and by a Pauli-paramagnetic contribution to the magnetic susceptibility. At room temperature, Na24-δ Ge136 slowly ages, with a tendency to volume decrease and sodium loss.

Reactivity and Controlled Redox Reactions of Salt-like Intermetallic Compounds in Imidazolium-Based Ionic Liquids.

Substituted imidazolium ionic liquids (ILs) were investigated for their reactivity towards Na12 Ge17 as a model system containing redox-sensitive Zintl cluster anions. The ILs proved widely inert for imidazolium cations with a 1,2,3-trisubstitution at least by alkyl groups, and for the anion bis(trifluoromethylsulfonyl)azanide (TFSI). A minute conversion of Na12 Ge17 observed on long-time contact with such ILs was not caused by dissolution of the salt-like compound, and did thus not provide dissolved Ge clusters. Rather, a cation exchange led to the transfer of Na+ ions into solution. In contrast, by using benzophenone as an oxidizer, heterogeneous redox reactions of Na12 Ge17 were initiated, transferring a considerable part of Na+ into solution. At optimized conditions, an X-ray amorphous product NaGe6.25 was obtained, which was thermally convertible to the crystalline type-II clathrate Na24-δ Ge136 with almost completely Na-filled polyhedral cages, and α-Ge. The presented method thus provides unexpected access to Na24-δ Ge136 in bulk quantities.

Expanding the Electrochemical Window: New Tunable Aryl Alkyl Ionic Liquids (TAAILs) with Dicyanamide Anions.

A set of new tunable aryl alkyl ionic liquids (TAAILs) based on the 1-aryl-3-alkyl imidazolium motif has been synthesized, in which the following variables were systematically changed: alkyl chain length, aryl substitution (group and position), and counter ion. TAAILs with dicyanamide (DCA) and bis(trifluoromethylsulfonyl)imide (N(SO2 CF3 )2 , NTf2 ) anions showed remarkable differences of their physical properties: NTf2 ionic liquids were found to have high decomposition temperatures and viscosities well below those of the DCA TAAILs. In contrast, the dicyanamide anion increased the electrochemical stability leading to TAAILs with an extremely wide electrochemical window of up to 7.17 V. Additionally, both classes of TAAILs extract transition metals from aqueous solutions: TAAILs with the DCA anion extract both platinum and copper while TAAILs with the NTf2 anion are selective towards platinum. This demonstrates that minor changes of the molecular structure lead to TAAILs with drastically changed physicochemical properties.

Aggregation control of Ru and Ir nanoparticles by tunable aryl alkyl imidazolium ionic liquids.

Metal-nanoparticles (M-NPs) were synthesized in a wet-chemical synthesis route in tunable aryl alkyl ionic liquids (TAAILs) based on the 1-aryl-3-alkyl-substituted imidazolium motif from Ru3(CO)12 and Ir4(CO)12 by microwave-heating induced thermal decomposition. The size and size dispersion of the NPs were determined by transmission electron microscopy (TEM) to an average diameter of 2.2(±0.1) to 3.9(±0.3) nm for Ru-NPs and to an average diameter of 1.4(±0.1) to 2.4(±0.1) nm for Ir-NPs. The TAAILs used contain the same bis(trifluoromethylsulfonyl)imide anion but differ in the substituents on the 1-aryl ring, e.g. 2-methyl-, 4-methoxy- and 2,4-dimethyl groups and in the 3-alkyl chain lengths (C4H9, C5H11, C8H17, C9H19, C11H23). All used TAAILs are suitable for the stabilization of Ru- and Ir-NPs over months in the IL dispersion. Different from all other investigations on M-NP/IL systems which we are aware of the particle separation properties of the TAAILs vary strongly as a function of the aryl substituent. Good NP separation can be achieved with the 4-methoxyphenyl- and 2,4-dimethylphenyl-substituted ILs, irrespective of the 3-alkyl chain lengths. Significant aggregation can be observed for 2-methylphenyl-substituted ILs. The good NP separation can be correlated with a negative electrostatic potential at the 4-methoxyphenyl or 4-methylphenyl substituent that is in the para-position of the aryl ring, whereas the 2-(ortho-)methylphenyl group assumes no negative potential. ε-ePC-SAFT calculations were used to validate that the interactions between ILs and the washing agents (required for TEM analyses) do not cause the observed aggregation/separation behaviour of the M-NPs. Ru-NPs were investigated as catalysts for the solvent-free hydrogenation of benzene to cyclohexane under mild conditions (70 °C, 10 bar) with activities up to 760 (mol cyclohexane) (mol Ru)-1 h-1 and over 95% conversion in ten consecutive runs for Ru-NPs. No significant loss of catalytic activity could be observed.

Cobalt-Catalyzed Hydroarylations and Hydroaminations of Alkenes in Tunable Aryl Alkyl Ionic Liquids.

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.