Nitrile-functionalized pyridinium ionic liquids: synthesis, characterization, and their application in carbon-carbon coupling reactions.

A series of relatively low-cost ionic liquids, based on the N-butyronitrile pyridinium cation [C(3)CNpy](+), designed to improve catalyst retention, have been prepared and evaluated in Suzuki and Stille coupling reactions. Depending on the nature of the anion, these salts react with palladium chloride to form [C(3)CNpy](2)[PdCl(4)] when the anion is Cl(-) and complexes of the formula [PdCl(2)(C(3)CNpy)(2)][anion](2) when the anion is PF(6)(-), BF(4)(-), or N(SO(2)CF(3))(2)(-). The solid-state structures of [C(3)CNpy]Cl and [C(3)CNpy](2)[PdCl(4)] have been established by single-crystal X-ray diffraction. The catalytic activity of these palladium complexes following immobilization in both N-butylpyridinium and nitrile-functionalized ionic liquids has been evaluated in Suzuki and Stille coupling reactions. All of the palladium complexes show good catalytic activity, but recycling and reuse is considerably superior in the nitrile-functionalized ionic liquid. Inductive coupled plasma spectroscopy reveals that the presence of the coordinating nitrile moiety in the ionic liquid leads to a significant decrease in palladium leaching relative to simple N-alkylpyridinium ionic liquids. Palladium nanoparticles have been identified as the active catalyst in the Stille reaction and were characterized using transmission electron microscopy.