A Stable Crystalline Copper(I)–N2O Complex Stabilized as the Salt of a Weakly Coordinating Anion

Abstract Nitrous oxide is considered a poor ligand, and therefore only a handful of well-defined metal?N2O complexes are known. Oxidation of copper powder with an extreme oxidant, [Ag2I2][An]2 ([An]?=[Al(OC(CF3)3)4]?) in perfluorinated hexane leads to CuI[An], the first auxiliary ligand-free CuI salt of the perfluorinated alkoxyaluminate anion. The compound is capable of forming a stable and crystalline complex with nitrous oxide, Cu(N2O)[An], where the Cu?N2O bond is by far the strongest among all other molecular metal?N2O complexes known. Thorough characterization of the compounds together with the crystal structure of Cu(N2O)[An] complex supported with DFT calculations are presented. These give insight into the bonding in the Cu+?N2O system and confirm N-end coordination of the ligand.