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

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 Cu-I[An], the first auxiliary ligand-free Cu-I 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.