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Treatment of LiC6F5 with B(C6F5)3 in equal volumes of light petroleum and diethyl ether at low temperature followed by slow warming to room temperature precipitates a microcrystalline solid which dries under vacuum to a material with the composition [Li(OEt2)3][B(C6F5)4]. Crystallization from diethyl ether yields solvent dependent [Li(OEt2)4][B(C6F5)4], which has been crystallographically characterised.

Several alcohols possessing alkali-labile substituents such as halogen, ester and ketone were effectively benzylated with benzyl mesylate by using a catalytic amount of lithium tetrakis(pentafluorophenyl)borate [LiB(C6F5)4] in the coexistence of lithium triflate (LiOTf) and magnesium oxide (MgO) to afford the corresponding benzyl ethers in good to excellent yields.

The title compound, Li+·C24BF20−·2C6H6, crystallizes as centrosymmetric dimers, with two η6-coordinated and two uncoordinated mol­ecules of benzene per dimer. There are two crystallographically independent dimers.

Several alcohols possessing alkali-labile substituents such as halogen, ester and ketone were effectively benzylated with benzyl mesylate by using a catalytic amount of lithium tetrakis(pentafluorophenyl)borate [LiB(C6F5)4] in the coexistence of lithium triflate (LiOTf) and magnesium oxide (MgO) to afford the corresponding benzyl ethers in good to excellent yields.

Lithium tetrakis(pentafluorophenyl)borate [LiB(C6F5)4], a neutral salt, effectively catalyzed Friedel–Crafts benzylation reactions of aromatic compounds with benzyl chloride or mesylate and their substituted derivatives. The LiB(C6F5)4-catalyzed reactions proceeded more efficiently in the coexistence of magnesium oxide.