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. Thorough characterization of the compounds together with the crystal structure of Cu(N O)[An] complex supported with DFT calculations are presented. These give insight into the bonding in the Cu -N O system and confirm N-end coordination of the ligand.
A comprehensive study of Ag+ and Cu+ complexes with weakly basic solvents stabilized by [Al{OC(CF3)3}4]− reveals their unique character and aids their applicability in further studies.
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.
Developments in the chemistry of weakly coordinating anions enabled isolation of numerous unique metal complexes with unusual ligands. An important example is the family of metal‐Fe(CO)5 complexes. In the current paper we present synthesis and thorough characterization of the first truly homoleptic {Cu[Fe(CO)5]2}+ cation obtained as a salt of weakly coordinating [Al(ORF)4]− (RF=C(CF3)3) anion. TGA/DSC/MS study show that its decomposition becomes noticeable only above 110 °C, thus it can be stored as powder in air‐free conditions for months. The crystal structure of {Cu[Fe(CO)5]2}+ shows strong asymmetry of the cation and very short Cu‐CO bonds in comparison to analogous {M[Fe(CO)5]2}+ where M=Ag or Au. Characterization is complemented with analysis of vibrational spectra and extensive DFT calculations which give insight into the energetics of Cu+‐Fe(CO)5 systems. Our results show that {Cu[Fe(CO)5]2}+ is homoleptic only as salt of [Al(ORF)4]−. Furthermore, in the presence of additional, even weakly basic ligands, the Cu+‐Fe(CO)5 bond strength decreases what may contribute to the complex's instability in liquid SO2 or in the presence of [SbF6]−. These conclusions point at the key role of selection of proper anion and solvent in stabilization of these types of complexes.
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