No abstract

Stable salts of the first homoleptic Cu-phosphorus and Cu-ethene complexes, [Cu(eta2-P4)2]+ and [Cu(eta2-C2H4)3]+, isolated by the aid of the weakly coordinating anion (WCA) [Al(OC(CF3)3)4]-, were obtained.

The uptake of simple gases by metal ions is of great current interest because of possible applications in gas storage and in gas activation reactions. Owing to the easier access, homoleptic metal complexes of simple gases were predominantly studied by mass spectrometry (MS)

Compounds including the free or coordinated gas-phase cations [Ag(eta(2)-C(2)H(4))(n)](+) (n = 1-3) were stabilized with very weakly coordinating anions [A](-) (A = Al{OC(CH(3))(CF(3))(2)}(4), n = 1 (1); Al{OC(H)(CF(3))(2)}(4), n = 2 (3); Al{OC(CF(3))(3)}(4), n = 3 (5); {(F(3)C)(3)CO}(3)Al-F-Al{OC(CF(3))(3)}(3), n = 3 (6)). They were prepared by reaction of the respective silver(I) salts with stoichiometric amounts of ethene in CH(2)Cl(2) solution. As a reference we also prepared the isobutene complex [(Me(2)C=CH(2))Ag(Al{OC(CH(3))(CF(3))(2)}(4))] (2). The compounds were characterized by multinuclear solution-NMR, solid-state MAS-NMR, IR and Raman spectroscopy as well as by their single crystal X-ray structures. MAS-NMR spectroscopy shows that the [Ag(eta(2)-C(2)H(4))(3)](+) cation in its [Al{OC(CF(3))(3)}(4)](-) salt exhibits time-averaged D(3h)-symmetry and freely rotates around its principal z-axis in the solid state. All routine X-ray structures (2theta(max.) < 55 degrees) converged within the 3sigma limit at C=C double bond lengths that were shorter or similar to that of free ethene. In contrast, the respective Raman active C=C stretching modes indicated red-shifts of 38 to 45 cm(-1), suggesting a slight C=C bond elongation. This mismatch is owed to residual librational motion at 100 K, the temperature of the data collection, as well as the lack of high angular data owing to the anisotropic electron distribution in the ethene molecule. Therefore, a method for the extraction of the C=C distance in [M(C(2)H(4))] complexes from experimental Raman data was developed and meaningful C=C distances were obtained. These spectroscopic C=C distances compare well to newly collected X-ray data obtained at high resolution (2theta(max.) = 100 degrees) and low temperature (100 K). To complement the experimental data as well as to obtain further insight into bond formation, the complexes with up to three ligands were studied theoretically. The calculations were performed with DFT (BP86/TZVPP, PBE0/TZVPP), MP2/TZVPP and partly CCSD(T)/AUG-cc-pVTZ methods. In most cases several isomers were considered. Additionally, [M(C(2)H(4))(3)] (M = Cu(+), Ag(+), Au(+), Ni(0), Pd(0), Pt(0), Na(+)) were investigated with AIM theory to substantiate the preference for a planar conformation and to estimate the importance of sigma donation and pi back donation. Comparing the group 10 and 11 analogues, we find that the lack of pi back bonding in the group 11 cations is almost compensated by increased sigma donation.

More than 50 years after the proposal of the Dewar–Chatt–Duncanson model for the binding of olefins to transition‐metal atoms, the first structurally characterized example of a silver–C2H4 complex ([Ag(η2‐C2H4)3]+, see picture) was obtained with the help of the very weakly coordinating [Al{OC(CF3)3}4]− ion. By contrast, earlier gas‐phase investigations only suggested the existence of [Ag(η2‐C2H4)x]+ ions (x=1 and 2).

The Li alkoxide LiORF (1) (RF = C(CF3)3) was quantitatively prepared by reacting stoichiometric amounts of LiH and HORF. Upon reaction of 1 with 1 equiv of AgBF4, the first donor-free Ag(I) alkoxide AgORF formed in 86% yield. The Ag alkoxide was then used for the preparation of trigonal bipyramidal [(AgL)3(ORF)2]+ cage cations (L = C2H4 (3), C4H8 (4)) stabilized by weakly coordinating [Al(ORF)4]- counterions. 1 to 4 were characterized by multinuclear NMR, IR, and Raman spectroscopy as well as by their single-crystal X-ray structures and additional quantum chemical calculations.

Keywords: Acidity / Aluminum / Brønsted acids / IR spectroscopy / Hydrogen bonds

Starke Komplexe dank schwacher Anionen: Die Festkörperstrukturen der ersten homoleptischen Metall‐HCCH‐Komplexe [M(C2H2)x]n+ (M=beliebiges Metall; n, x=beliebige Zahl) in Form zweier [Ag(η2‐C2H2)n]+‐Salze (n=3, 4) werden beschrieben (siehe Bild). Zudem gelang es, die elektronische Struktur einer [Ag(η2‐C2H2)]+‐Modellverbindung durch experimentelle Ladungsdichtestudien zu untersuchen.