Critical Role of Nonrigid Unit and Spiral Acoustical Modes in Designing Colossal Negative Thermal Expansion.

Exploring the relationship between thermal expansion and structural complexity is a challenging topic in the study of modern materials where volume stability is required. This work reports a new family of negative thermal expansion (NTE) materials, AM(CN)4 with A = Li and Na and M = B, Al, Ga, and In. Here, the compounds of LiB(CN)4 and NaB(CN)4 were only synthesized; others were purely computationally studied. A critical role of nonrigid vibrational modes and spiral acoustical modes has been identified in NaB(CN)4. This understanding has been exploited to design the colossal NTE materials of NaM(CN)4 (M = Al, Ga, In). A joint study involving synchrotron X-ray diffraction, Raman spectroscopy, and first-principles calculations has been conducted to investigate the thermal expansion mechanism. It has been found that the A atoms can either increase the symmetry of the crystal structure, inducing stronger NTE, or lower the crystal symmetry, thus resulting in positive thermal expansion. Conversely, the M-site atoms do not affect the crystal structure. However, as the radius of the M atoms increases, the ionic nature of the C-M bonds strengthens and the CN vibrations become more flexible, thereby enhancing the NTE behavior. This study provides new insights to aid in the discovery and design of novel NTE materials and the control of thermal expansion.

Nickel(II) Cyanoborates and Cyanoborate-Ligated Nickel(II) Complexes.

Nickel(II) cyanoborates Ni[BH2(CN)2]2·H2O (1b·H2O), Ni[BH(CN)3]2·0.5H2O (1c·0.5H2O), and Ni[B(CN)4]2·0.5H2O (1d·0.5H2O) were synthesized, and their reactivity with respect to dppeO2 (=1,2-bis-(diphenylphosphinoethane dioxide)), pyNO (=pyridine-N-oxide), dppe (=1,2-bis-(diphenylphosphinoethane), and DMSO (=dimethyl sulfoxide) was examined. Using these ligands, either cyanoborate (CB) complex salts of [Ni(dppe)2]2+ (2b-d) and [Ni(pyNO)6]2+ (3c-d) were isolated or complexes [Ni(DMSO)4{NC-B(CN)3}2] (1dDMSO) and [Ni(dppeO2)2{NC-B(CN)3}2] (1ddppeO2) were formed. Salt metathesis of [Ni(dppe)Cl2] with alkali metal cyanoborates resulted in mono- and disubstituted coordination compounds [Ni(dppe){NC-BH(CN)2}Cl] (5c) and [Ni(dppe){NC-BH2CN)2}] (4b), which decomposed to salts 2b-d. The synthetical pathways explored offer convenient routes to nickel(II) cyanoborates, nickel(II) complexes ligated with cyanoborates, and nickel(II) complex salts of cyanoborates. Further, our studies demonstrate the diverse character of cyanoborates in coordination chemistry as noncoordinating counteranions and also as medium coordinating anions forming novel transition-metal complexes and salts.

Giant Negative Thermal Expansion in Ultralight NaB(CN)4.

Negative thermal expansion (NTE) is crucial for controlling the thermomechanical properties of functional materials, albeit being relatively rare. This study reports a giant NTE (αV ∼-9.2 ⋅ 10-5  K-1 , 100-200 K; αV ∼-3.7 ⋅ 10-5  K-1 , 200-650 K) observed in NaB(CN)4 , showcasing interesting ultralight properties. A comprehensive investigation involving synchrotron X-ray diffraction, Raman spectroscopy, and first-principles calculations has been conducted to explore the thermal expansion mechanism. The findings indicate that the low-frequency phonon modes play a primary role in NTE, and non-rigid vibration modes with most negative Grüneisen parameters are the key contributing factor to the giant NTE observed in NaB(CN)4 . This work presents a new material with giant NTE and ultralight mass density, providing insights for the understanding and design of novel NTE materials.

Alkylcyanoborate Anions: Building Blocks for Fluorine-Free Low-Viscosity, Electrochemically and Thermally Stable Ionic Liquids.

A set of mixed-substituted potassium alkylcyano- and alkylcyanofluoroborates has been synthesized using easily accessible starting compounds and characterized by elemental analysis, NMR and vibrational spectroscopy, and mass spectrometry. In addition, single-crystal structures of salts of the cyanoborate anions have been derived from X-ray diffraction experiments. The 1-ethyl-3-methylimidazolium room temperature ionic liquids ([EMIm]+ -RTILs) with the new borate anions have been synthesized and their physicochemical properties, that is, high thermal and electrochemical stability, low viscosity, and high conductivity, have been compared to the properties of related [EMIm]+ -RTILs. The influence of the different alkyl substituents at boron has been assessed. The exemplary study on the properties with the [EMIm]+ -ILs with the mixed water stable alkylcyanoborate anions points towards the potential of these fluorine-free borate anions, in general.

Synthesis of Partially Fluorinated Alkyl Triflates by Electrochemical Fluorination (Simons Process).

A scalable straightforward synthesis of monofluoro- and difluoromethyl triflate CF3 SO2 OCH2 F (MH2F ) and CF3 SO2 OCHF2 (MHF2 ) through electrochemical fluorination (ECF, Simons process) of methyl triflate MH3 in anhydrous hydrogen fluoride at nickel anodes is presented. The ECF method is also feasible for the preparation of the deuterated analogues CF3 SO2 OCD2 F (MD2F ) and CF3 SO2 OCDF2 (MD2F ). Surprisingly, no H/D exchange occurs during ECF of CF3 SO2 OCD3 (MD3 ); this provides further evidence for a NiF3 /NiF4 -mediated ECF mechanism. The ECF of selected partially fluorinated ethyl triflates is described, and electrochemical fluorination of CF3 SO2 OCH2 CF3 (EH2F3 ) leads to the until now unknown chiral CF3 SO2 OCHFCF3 (EHFF3 ). The analogous fluoromethyl and fluoroethyl nonaflates are also accessible by ECF. This study contains detailed spectroscopic, structural, and thermal data on (fluoro)methyl and fluoro(ethyl) triflates.

Cyano(fluoro)borate and cyano(hydrido)borate ionic liquids: low-viscosity ionic media for electrochemical applications.

The synthesis and detailed characterization of low-viscosity room-temperature ionic liquids (RTILs) and [BnPh3P]+ salts with the cyano(fluoro)borate anions [BF(CN)3]- (MFB), [BF2(CN)2]- (DFB), and [BF3(CN)]- as well as the new mixed-substituted anion [BFH(CN)2]- (FHB) is described. The RTILs with [EMIm]+ or [BMPL]+ as countercations were obtained in yields of up to 98% from readily available alkali metal salts and in high purities that allow application in electrochemical devices. Trends in thermal stability, melting and freezing behavior, density, electrochemical stability, dynamic viscosity, specific conductivity and ion diffusivity have been assessed and compared to those of the related tetracyanoborate- and cyano(hydrido)borate-RTILs. The crystal structure analysis of the [BnPh3P]+ salts of [BFn(CN)4-n]- (n = 0-4), [BHn(CN)4-n]- (n = 1-3) and [BFH(CN)2]- provided experimental access to anion volumina that together with ion molecular mass, electrostatic potential, shape and chemical stability have been correlated to physicochemical properties. In addition, the cytotoxicity of the [EMIm]+-ILs and potassium or sodium salts was studied.

Innovative Syntheses of Cyano(fluoro)borates: Catalytic Cyanation, Electrochemical and Electrophilic Fluorination.

Different types of high-yield, easily scalable syntheses for cyano(fluoro)borates Kt[BFn (CN)4-n ] (n=0-2) (Kt=cation), which are versatile building blocks for materials applications and chemical synthesis, have been developed. Tetrafluoroborates react with trimethylsilyl cyanide in the presence of metal-free Brønsted or Lewis acid catalysts under unprecedentedly mild conditions to give tricyanofluoroborates or tetracyanoborates. Analogously, pentafluoroethyltrifluoroborates are converted into pentafluoroethyltricyanoborates. Boron trifluoride etherate, alkali metal salts, and trimethylsilyl cyanide selectively yield dicyanodifluoroborates or tricyanofluoroborates. Fluorination of cyanohydridoborates is the third reaction type that includes direct fluorination with, for example, elemental fluorine, stepwise halogenation/fluorination reactions, and electrochemical fluorination (ECF) according to the Simons process. In addition, fluorination of [BH(CN)2 {OC(O)Et}]- to result in [BF(CN)2 {OC(O)Et}]- is described.

Thermal Decomposition and Hypergolic Reaction of a Dicyanoborohydride Ionic Liquid.

In this study, in situ infrared spectroscopy techniques and thermogravimetric analysis coupled with mass spectrometry (TGA-MS) are employed to characterize the reactivity of the ionic liquid, 1-butyl-3-methylimidazolium dicyanoborohydride (BMIM+DCBH-), in comparison to the well-characterized 1-butyl-3-methylimidazolium dicyanamide (BMIM+DCA-) ionic liquid. TGA measurements determined the enthalpy of vaporization (ΔHvap) to be 112.7 ± 12.3 kJ/mol at 298 K. A rapid scan Fourier transform infrared spectrometer was used to obtain vibrational information useful in tracking the appearance and disappearance of species in the hypergolic reactions of BMIM+DCBH- and BMIM+DCA- with white fuming nitric acid (WFNA) and in the thermal decomposition of these energetic ionic liquids. Attenuated total reflectance measurements recorded the infrared spectra of the reactant sample (BMIM+DCBH-) and the liquid reaction products after reacting with WFNA. Computational chemistry efforts, aided by the experimental results, were used to propose key reaction pathways leading to the hypergolic ignition of BMIM+DCBH- + WFNA. Experimental results indicate that the hypergolic reaction of BMIM+DCBH- with WFNA generates both common and unique intermediates as compared to previous BMIM+DCA- + WFNA investigations: nitrous oxide was generated during both hypergolic reactions indicating that it may play a crucial role in the hypergolic ignition process, NO2 was generated in significantly higher concentrations for BMIM+DCBH- than for BMIM+DCA-, CO2 was only generated for BMIM+DCA-, and HCN was only generated during thermal decomposition and hypergolic ignition of BMIM+DCBH-.

Cyanohydridoborate Anions: Synthesis, Salts, and Low-Viscosity Ionic Liquids.

High-yield syntheses up to molar scales for salts of [BH(CN)3 ]- (2) and [BH2 (CN)2 ]- (3) starting from commercially available Na[BH4 ] (Na5), Na[BH3 (CN)] (Na4), BCl3 , (CH3 )3 SiCN, and KCN were developed. Direct conversion of Na5 into K2 was accomplished with (CH3 )3 SiCN and (CH3 )3 SiCl as a catalyst in an autoclave. Alternatively, Na5 is converted into Na[BH{OC(O)R}3 ] (R=alkyl) that is more reactive towards (CH3 )3 SiCN and thus provides an easy access to salts of 2. Some reaction intermediates were identified, for example, Na[BH(CN){OC(O)Et}2 ] (Na7 b) and Na[BH(CN)2 {OC(O)Et}] (Na8 b). A third entry to 2 and 3 uses ether adducts of BHCl2 or BH2 Cl such as the commercial 1,4-dioxane adducts that react with KCN and (CH3 )3 SiCN. Alkali metal salts of 2 and 3 are convenient starting materials for organic salts, especially for low viscosity ionic liquids (ILs). [EMIm]3 has the lowest viscosity and highest conductivity with 10.2 mPa s and 32.6 mS cm-1 at 20 °C known for non-protic ILs. The ILs are thermally, chemically, and electrochemically robust. These properties are crucial for applications in electrochemical devices, for example, dye-sensitized solar cells (Grätzel cells).

Hydroxytricyanoborate Anion: Synthetic Aspects and Structural, Chemical, and Spectroscopic Properties.

In recent years, salts of the hydridotricyanoborate anion [BH(CN)3]- (MHB) have become readily available. In spite of the unusually high stability of the MHB anion, it can be used as a valuable starting material for the preparation of selected tricyanoborates, for example, the boron-centered nucleophile B(CN)32-. A further unprecedented example is the hydroxytricyanoborate anion [B(OH)(CN)3]- that is accessible by oxidation of (H3O)MHB with elemental bromine in water. The Brønsted acid (H3O)[B(OH)(CN)3] was isolated as a crystalline solid. It serves as a versatile starting material for the synthesis of coordination compounds, metal salts, and ionic liquids. The [B(OH)(CN)3]- anion shows a rich coordination chemistry and a high tendency to form hydrogen-bonded motifs as demonstrated by a series of salts with different types of cations. Furthermore, the [B(OH)(CN)3]- anion itself serves as starting material for new tricyanoborates such as the unusual trianion [B{OB(CN)3}3]3- and the silylated anions [B(OSiR3)(CN)3]- (R = Me, Et, Ph). Some of these follow-up products have been characterized by single-crystal X-ray diffraction, e.g., [nBu4N]3[B{OB(CN)3}3] and [nBu4N][B(OSiPh3)(CN)3].

Oxidation of a Levitated 1-Butyl-3-methylimidazolium Dicyanoborate Droplet by Nitrogen Dioxide.

To develop the next generation of hypergolic, ionic-liquid-based fuels, it is important to understand the fundamental reaction mechanisms for the oxidation of ionic liquids (ILs). We consequently studied the oxidation of a levitated 1-butyl-3-methylimidazolium dicyanoborate ([BMIM][DCBH]) droplet by nitrogen dioxide (NO2). The properties of [BMIM][DCBH], including short ignition-delay times, low viscosities, and a wide liquid temperature range, make the ionic liquid especially suitable as a component of a hypergolic fuel. The chemical modifications were monitored with Fourier-transform infrared (FTIR), Raman, and ultraviolet-visible spectroscopies. To identify changes induced by the oxidation, it was first necessary to assign vibrational modes to the FTIR and Raman spectra of unreacted [BMIM][DCBH]. The new features in the oxidized FTIR and Raman spectra could then be identified and assigned on the basis of the possible functional groups likely to form through addition with a nitrogen and an oxygen atom of nitrogen dioxide creating a new bond with the ionic liquid. The assignments suggest that organic nitro-compounds and boron-nitrogen and boron-oxygen containing compounds were produced. A large decrease in the intensity of some [DCBH]- fundamental modes suggests the nitrogen dioxide molecule prefers to react with the anion over the cation.

The Role of [BF4 ]- and [B(CN)4 ]- Anions in the Ionothermal Synthesis of Chalcogenidometalates.

The role of borate anions in ionothermal syntheses of crystalline chalcogenidometalates was shown by the directed ionothermal synthesis of seven new selenidostannates in ionic liquids with either [BF4 ]- or [B(CN)4 ]- anions. Single crystal structures are presented of four compounds, (C4 C1 C1 Im)5 [Sn9 Se20 ][BF4 ] (1, Im=imidazolium), (DMMPH)4 [Sn2 Se6 ] (2, DMMP=2,6-dimethylmorpholine), (C2 C1 Im)2 (DMMPH)2 [Sn6 Se14 ] (3), and K2 [Sn3 Se7 ] (4), and how the chosen ionic liquid anion, and the reaction temperature, influences the product spectrum is discussed: Notably, 1 contains an entire formula unit of the ionic liquid, (C4 C1 C1 Im)[BF4 ], while 4 contains neither the cation nor the anion of the ionic liquid-both observations being very uncommon for ionothermal syntheses. Three further compounds were obtained that exhibit strong disorder in the crystal structures (I-III), for which only their anionic substructures are discussed herein. Compound 4 and I-III are based on the same layered selenidostannate substructure, 2D-{[Sn3 Se7 ]2- }, yet with different inter-layer distances, which is clearly reflected in the crystal colors and quantitative optical absorption properties.

Perfluoroalkyltricyanoborate and Perfluoroalkylcyanofluoroborate Anions: Building Blocks for Low-Viscosity Ionic Liquids.

The potassium perfluoroalkyltricyanoborates K[Cn F2 n+1 B(CN)3 ] [n=1 (1 d), 2 (2 d)] and the potassium mono(perfluoroalkyl)cyanofluoroborates K[Cn F2 n+1 BF(CN)2 ] [n=1 (1 c), 2 (2 c)] and [Cn F2 n+1 BF2 (CN)]- [n=1 (1 b), 2 (2 b), 3 (3 b), 4 (4 b)] are accessible with perfect selectivities on multi-gram scales starting from K[Cn F2 n+1 BF3 ] and Me3 SiCN. The K+ salts are starting materials for the preparation of salts with organic cations, for example, [EMIm]+ (EMIm=1-ethyl-3-methylimidazolium). These [EMIm]+ salts are hydrophobic room-temperature ionic liquids (RTILs) that are thermally, chemically and electrochemically very robust, offering electrochemical windows up to 5.8 V. The RTILs described herein, exhibit very low viscosities with a minimum of 14.0 mPa s at 20 °C for [EMIm]1 c, low melting points down to -57 °C for [EMIm]2 b and extraordinary high conductivities up to 17.6 mS cm-1 at 20 °C for [EMIm]1 c. The combination of these properties makes these ILs promising materials for electrochemical devices as exemplified by the application of selected RTILs as component of electrolytes in dye-sensitised solar cells (DSSCs, Grätzel cells). The efficiency of the DSSCs was found to increase with a decreasing viscosity of the neat ionic liquid. In addition to the spectroscopic characterisation, single crystals of the potassium salts of the anions 1 b-d, 2 d, 3 b and 4 c as well as of [nBu4 N]2 c have been studied by X-ray diffraction.

Formation of a Trifluorophosphane Platinum(II) Complex by P-F Bond Activation of Phosphorus Pentafluoride with a Pt0 Complex.

The reaction of PF5 with [(Cy3 P)2 Pt] gave the PF3 complex trans-[(Cy3 P)2 PtF(PF3 )][PF6 ], which was characterized by single-crystal X-ray diffraction, multinuclear NMR spectroscopy, and elemental analysis. To the best of our knowledge, this reaction is the first example of the oxidative addition of a P-F bond to a transition metal and is a rare example of an activation of a main-group-element-fluorine bond by a metal. Relativistic DFT calculations showed that the formation of the Lewis pair [(Cy3 P)2 Pt→PF5 ], which was not observed even at low temperatures, represents the initial step of the reaction. From this key intermediate, the cation trans-[(Cy3 P)2 PtF(PF3 )]+ was furnished by a two-step mechanism involving, successively, a second and a third PF5 molecule.

Deprotonation of a Hydridoborate Anion.

The first deprotonation of a borohydride anion was achieved by treatment of [BH(CN)3 ]- with strong non-nucleophilic bases, which resulted in the formation of alkali-metal salts of the tricyanoborate dianion B(CN)32- in up to 97 % yield and 99.5 % purity. [BH(CN)3 ]- is less acidic than (Me3 Si)2 NH but a stronger acid than iPr2 NH. Less sterically hindered, more nucleophilic bases such as PhLi and MeLi mostly attack a CN group under formation of imine dianions [RC(N)B(CN)3 ]2- , which can be hydrolyzed to ketones of the [RC(O)B(CN)3 ]- type. The boron-centered nucleophile B(CN)32- reacts with CO2 and CN+ reagents to give salts of the [B(CN)3 CO2 ]2- dianion and the tetracyanoborate anion [B(CN)4 ]- , respectively, in excellent yields.

Protonation versus Oxonium Salt Formation: Basicity and Stability Tuning of Cyanoborate Anions.

Anhydrous H[BH2 (CN)2 ] crystallizes from acidic aqueous solutions of the dicyanodihydridoborate anion. The formation of H[BH2 (CN)2 ] is surprising as the protonation of nitriles requires strongly acidic and anhydrous conditions but it can be rationalized based on theoretical data. In contrast, [BX(CN)3 ]- (X=H, F) gives the expected oxonium salts (H3 O)[BX(CN)3 ] while (H3 O)[BF2 (CN)2 ]/H[BF2 (CN)2 ] is unstable. H[BH2 (CN)2 ] forms chains via N-H⋅⋅⋅N bonds in the solid state and melts at 54 °C. Solutions of H[BH2 (CN)2 ] in the room-temperature ionic liquid [EMIm][BH2 (CN)2 ] contain the [(NC)H2 BCN-H⋅⋅⋅NCBH2 (CN)]- anion and are unusually stable, which enabled the study of selected spectroscopic and physical properties. [(NC)H2 BCN-H⋅⋅⋅NCBH2 (CN)]- slowly gives H2 and [(NC)H2 BCN-BH(CN)2 ]- . The latter compound is a source of the free Lewis acid BH(CN)2 , as shown by the generation of [BHF(CN)2 ]- and BH(CN)2 ⋅py.

Syntheses of tricyanofluoroborates M[BF(CN)3] (M = Na, K): (CH3)3SiCl catalysis, countercation effect, and reaction intermediates.

Potassium tricyanofluoroborate, K[BF(CN)3], which is the starting material for tricyanofluoroborate room-temperature ionic liquids [N. Ignat'ev et al. J. Fluorine Chem., submitted] was obtained on a molar scale (140 g) from Na[BF4] and (CH3)3SiCN with a purity of up to 99.9%. The initial product of the reaction that was catalyzed by (CH3)3SiCl was Na[BF(CN)3]·(CH3)3SiCN that was characterized by multinuclear NMR and vibrational spectroscopy, elemental analysis, differential scanning calorimetry, and single-crystal X-ray diffraction. Na[BF(CN)3]·(CH3)3SiCN was converted to K[BF(CN)3] via a simple extraction protocol. The catalytic effect of (CH3)3SiCl was evaluated and some intermediates of the reaction, including the isocyanoborate anion [BF(NC)(CN)2](-), were identified using multinuclear NMR and vibrational spectroscopy. K[BF2(CN)2] also reacted with (CH3)3SiCN in the presence of (CH3)3SiCl, to result in K[BF(CN)3]. The interpretation of the experimental observations was supported by data derived from density functional theory (DFT) calculations. In addition, the influence of selected countercations of the tetrafluoroborate anion on the progress of the (CH3)3SiCl-catalyzed reaction was studied. The fastest reaction was observed for Na[BF4], while the conversion of [BF4](-) to [BF(CN)3](-) was slower with the countercation K(+). Li[BF4] and [Et4N][BF4] were converted under the reaction conditions applied to Li[BF2(CN)2] and [Et4N][BF2(CN)2] only.

The hexacyanodiborane(6) dianion [B2(CN)6](2-).

Diborane(6) dianions with substituents that are bonded to boron via carbon are very reactive and therefore only a few examples are known. Diborane(6) derivatives are the simplest catenated boron compounds with an electron-precise B-B σ-bond that are of fundamental interest and of relevance for material applications. The homoleptic hexacyanodiborane(6) dianion [B2 (CN)6 ](2-) that is chemically very robust is reported. The dianion is air-stable and resistant against boiling water and anhydrous hydrogen fluoride. Its salts are thermally highly stable, for example, decomposition of (H3 O)2 [B2 (CN)6 ] starts at 200 °C. The [B2 (CN)6 ](2-) dianion is readily accessible starting from 1) B(CN)3 (2-) and an oxidant, 2) [BF(CN)3 ](-) and a reductant, or 3) by the reaction of B(CN)3 (2-) with [BHal(CN)3 ](-) (Hal=F, Br). The latter reaction was found to proceed via a triply negatively charged transition state according to an SN 2 mechanism.

Insights into structure-property relationships in ionic liquids using cyclic perfluoroalkylsulfonylimides.

Room temperature ionic liquids of cyclic sulfonimide anions ncPFSI (ring size: n = 4-6) with the cations [EMIm]+ (1-ethyl-3-methylimidazolium), [BMIm]+ (1-butyl-3-methylimidazolium) and [BMPL]+ (BMPL = 1-butyl-1-methylpyrrolidinium) have been synthesized. Their solid-state structures have been elucidated by single-crystal X-ray diffraction and their physicochemical properties (thermal behaviour and stability, dynamic viscosity and specific conductivity) have been assessed. In addition, the ion diffusion was studied by pulsed field gradient stimulated echo (PFGSTE) NMR spectroscopy. The decisive influence of the ring size of the cyclic sulfonimide anions on the physicochemical properties of the ILs has been revealed. All ILs show different properties compared to those of the non-cyclic TFSI anion. While these differences are especially distinct for ILs with the very rigid 6cPFSI anion, the 5-membered ring anion 5cPFSI was found to result in ILs with relatively similar properties. The difference between the properties of the TFSI anion and the cyclic sulfonimide anions has been rationalized by the rigidity (conformational lock) of the cyclic sulfonimide anions. The comparison of selected IL properties was augmented by MD simulations. These highlight the importance of π+-π+ interactions between pairs of [EMIm]+ cations in the liquid phase. The π+-π+ interactions are evident for the solid state from the molecular structures of the [EMIm]+-ILs with the three cyclic imide anions determined by single-crystal X-ray diffraction.

Ethyl-, vinyl- and ethynylcyanoborates: room temperature borate ionic liquids with saturated and unsaturated hydrocarbon chains.

Ethyl-, vinyl- and ethynyltricyano and dicyanofluoroborates were prepared on a gram scale from commercially available potassium trifluoroborates and trimethylsilylcyanide. Salt metathesis resulted in the corresponding EMIm-salts that are hydrophobic room-temperature ionic liquids (RTILs). The new RTILs exhibit unprecedented large electrochemical windows in combination with high thermal stabilities, low dynamic viscosities and high specific conductivities. These properties make them promising materials, especially for electrochemical applications.