The hydrophobic, low melting, 1‐butyl‐3‐methylimidazolium (BMIm) salts [BMIm][BPh4] (1), [BMIm][B(C6H4Me‐4)4] (2), [BMIm][B{C6H4(CF3)‐4}4] (3), [BMIm][B{C6H3(CF3)2‐3,5}4] (4), [BMIm][B{C6H4(C6F13)‐4}4] (5), [BMIm][B{C6H4(SiMe3)‐4}4] (6), [BMIm][B(C6H4{SiMe2(CH2CH2CF3)}‐4)4] (7), [BMIm][B{C6H4(SiMe2C8H17}‐4}4] (8) and [BMIm][B(C6H4{SiMe2(CH2CH2C6F13)}‐4)4] (9) have been prepared. Systematic variation of the substituents on the tetraphenylborate anion allowed an assessment of their influence on the physical properties of the imidazolium salts. Structural investigations using NMR and IR spectroscopy, combined with single crystal X‐ray structure determinations for 2, 3, 5 and 6, revealed hydrogen‐bonding interactions between the imidazolium ring protons and the borate anion, both in the solid state and in solution. These interactions are weakened upon the introduction of electron‐withdrawing substituents in the anion and follow the order 3,5‐(CF3)2 < −C6F13 < −CF3 < −SiMe2CH2CH2C6F13 < −SiMe2CH2CH2CF3 < −H < −Me < −SiMe3. The melting points of the salts depend primarily on the bulk of the lipophilic substituents, and decrease with increasing size. Bulky lipophilic substituents dramatically enhance the solubility of the imidazolium borates 8 and 9 in hexane and reduce their relative polarity. These unique properties make imidazolium borates 8 and 9 interesting as amphiphilic ionic liquids with low polarity. Attempts to crystallise 7 resulted in decomposition. A single‐crystal X‐ray structure determination of the product, isolated in 6% yield, showed that a carbene−tris[4‐{dimethyl(3,3,3‐trifluoropropyl)silyl}phenyl]borane adduct was formed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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