Implications of the crystal structure of the ammonia solvate [Au(NH3)2]Cl·4NH3.

Crystals of diammine gold(I) chloride ammonia (1/4), [Au(NH(3))(2)]Cl·4NH(3), have been grown from solutions of AuCl in liquid ammonia. The X-ray diffraction analysis (at 123 K) has shown that the crystals feature an extensive network of hydrogen bonds between the [H(3)N-Au-NH(3)](+) cations (with C(i) symmetry) and the Cl(-) anions, including also the ammonia molecules. There is no evidence for an emerging increase of the coordination number of the gold atom by adopting another ammonia molecule or by approaching a chloride anion. Moreover, the geometry of two distant and angular N-H···Au contacts is not a strong support of hydrogen bonds recently amply discussed in the literature.

Reactions of beryllium halides in liquid ammonia: the tetraammineberyllium cation [Be(NH3)4]2+, its hydrolysis products, and the action of Be2+ as a fluoride-ion acceptor.

The first structural characterization of the text-book tetraammineberyllium(II) cation [Be(NH(3))(4)](2+), obtained in the compounds [Be(NH(3))(4)](2)Cl(4)⋅17NH(3) and [Be(NH(3))(4)]Cl(2), is reported. Through NMR spectroscopic and quantum chemical studies, its hydrolysis products in liquid ammonia were identified. These are the dinuclear [Be(2)(µ-OH)(NH(3))(6)](3+) and the cyclic [Be(2)(µ-OH)(2)(NH(3))(4)](2+) and [Be(3)(µ-OH)(3)(NH(3))(6)](3+) cations. The latter species was isolated as the compound [Be(3)(µ-OH)(3)(NH(3))(6)]Cl(3)⋅7NH(3). NMR analysis of solutions of BeF(2) in liquid ammonia showed that the [BeF(2)(NH(3))(2)] molecule was the only dissolved species. It acts as a strong fluoride-ion acceptor and forms the [BeF(3)(NH(3))](-) anion in the compound [N(2)H(7)][BeF(3)(NH(3))]. The compounds presented herein were characterized by single-crystal X-ray structure analysis, (9)Be, (17)O, and (19)F NMR, IR, and Raman spectroscopy, deuteration studies, and quantum chemical calculations. The extension of beryllium chemistry to the ammine system shows similarities but also decisive differences to the aquo system.

UF6 and UF4 in liquid ammonia: [UF7(NH3)]3- and [UF4(NH3)4].

From the reaction of uranium hexafluoride UF6 with dry liquid ammonia, the [UF7(NH3)]3- anion and the [UF4(NH3)4] molecule were isolated and identified for the first time. They are found in signal-green crystals of trisammonium monoammine heptafluorouranate(IV) ammonia (1:1; [NH4]3[UF7(NH3)].NH3) and emerald-green crystals of tetraammine tetrafluorouranium(IV) ammonia (1:1; [UF4(NH3)4].NH3). [NH4]3[UF7(NH3)].NH3 features discrete [UF7(NH3)]3- anions with a coordination geometry similar to a bicapped trigonal prism, hitherto unknown for U(IV) compounds. The emerald-green [UF4(NH3)4].NH3 contains discrete tetraammine tetrafluorouranium(IV) [UF4(NH3)4] molecules. [UF4(NH3)4].NH3 is not stable at room temperature and forms pastel-green [UF4(NH3)4] as a powder that is surprisingly stable up to 147 degrees C. The compounds are the first structurally characterized ammonia complexes of uranium fluorides.