A Stable Crystalline Copper(I)-N2 O 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-N2 O complexes are known. Oxidation of copper powder with an extreme oxidant, [Ag2 I2 ][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(N2 O)[An], where the Cu-N2 O bond is by far the strongest among all other molecular metal-N2 O complexes known. Thorough characterization of the compounds together with the crystal structure of Cu(N2 O)[An] complex supported with DFT calculations are presented. These give insight into the bonding in the Cu+ -N2 O system and confirm N-end coordination of the ligand.