Synthesis and Characterization of a Copper Dinitrogen Complex Supported by a Weakly Coordinating Anion.

We report the synthesis and full characterization of the copper dinitrogen complex [(η-N)Cu{Al(OR)}] 2 (R=C(CF)) prepared by a cascade metathesis reaction of Ag[Al(OR)] with CuI-excess in iso-perfluorohexane (i-pfh) under N atmosphere. Title compound 2 features an extraordinarily high N stretching frequency at 2313/2314 cm (IR/Raman) and was characterized by single-crystal and powder X-ray diffractometry. Quantum chemical charge displacement analysis based on natural orbitals of chemical valence (CD-NOCV) indicates that the copper-dinitrogen interaction is still governed by weak π-backdonation, but is significantly reduced compared to all literature-known transition metal dinitrogen complexes.

Extending the chemistry of weakly basic ligands: solvates of Ag and Cu stabilized by [Al{OC(CF)}] anion as model examples in the screening of useful weakly interacting solvents.

Weakly Coordinating Anions (WCAs) facilitate the formation of exotic "naked" cationic species. However, the feasibility of the respective synthesis approaches may be limited by the basicity of the solvent utilized, as the latter is one of the most important factors determining the solvation ability. In this work, we focus on a series of novel complexes of Ag(i) and Cu(i) with weakly basic ligands such as CHCl, ClCCN and SO stabilized by perfluorinated alkoxyaluminate, Al[(OR)], R = C(CF).

A Stable Crystalline Copper(I)-N 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 O complexes are known. Oxidation of copper powder with an extreme oxidant, [Ag I ][An] ([An] =[Al(OC(CF ) ) ] ) in perfluorinated hexane leads to Cu [An], the first auxiliary ligand-free Cu salt of the perfluorinated alkoxyaluminate anion. The compound is capable of forming a stable and crystalline complex with nitrous oxide, Cu(N O)[An], where the Cu-N O bond is by far the strongest among all other molecular metal-N O complexes known.