A Stable Crystalline Copper(I)–N 2 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–N 2 O complexes are known. Oxidation of copper powder with an extreme oxidant, [Ag 2 I 2 ][ An ] 2 ([ An ] − =[Al(OC(CF 3 ) 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(N 2 O)[ An ], where the Cu−N 2 O bond is by far the strongest among all other molecular metal–N 2 O complexes known. Thorough characterization of the compounds together with the crystal structure of Cu(N 2 O)[ An ] complex supported with DFT calculations are presented. These give insight into the bonding in the Cu + –N 2 O system and confirm N‐end coordination of the ligand.