Reactions of noble-metal oxides in ionic liquids near room temperature

Abstract

The reaction of Ag₂O, Au₂O₃, and HgO with CuCl, CuI, AgCl, AgI, AuCl, and AuI in ionic liquids ([EMIm]Cl, [BMIm]Cl) near room temperature (20–80 °C) is evaluated and results in the new compounds (C₈H₁₄N₂)CuCl, (C₈H₁₄N₂)AgI, (C₆H₁₀N₂)AuCl, [(C₈H₁₄N₂)₂Hg][CuCl₃], [(C₈H₁₄N₂)₂Hg][AgCl₃], and [EMIm][Ag₂I₂Cl]. Thereof, (C₈H₁₄N₂)CuCl, (C₈H₁₄N₂)AgI, (C₆H₁₀N₂)AuCl, [(C₈H₁₄N₂)₂Hg][CuCl₃], and [(C₈H₁₄N₂)₂Hg][AgCl₃] are NHC complexes (NHC: N-heterocyclic carbene) with M–C bonds (M: Cu, Ag, Au, Hg). Whereas (C₈H₁₄N₂)CuCl and (C₈H₁₄N₂)AgI crystallize as single molecules, (C₆H₁₀N₂)AuCl is dimerized via aurophilic interactions. [(C₈H₁₄N₂)₂Hg][CuCl₃] and [(C₈H₁₄N₂)₂Hg][AgCl₃] exhibit Hg atoms with two Hg–C bonds. Moreover, (C₈H₁₄N₂)AgI shows intense green fluorescence at room temperature with a quantum yield of 44%, whereas all other compounds do not show any emission at room temperature. Finally, [EMIm][Ag₂I₂Cl] is not an NHC compound but contains _∞¹[AgI_1/2I_2/4Cl_1/2]⁻ chains with infinite d¹⁰–d¹⁰ interaction of the silver atoms. The title compounds are characterized by single-crystal structure analysis, infrared spectroscopy, thermogravimetry, and fluorescence spectroscopy.