From the dark‐purple solution of the Zintl phase KBi in liquid ammonia dark‐blue crystals of the ammonia solvate K6[Bi4](NH3)8 were obtained. In contrast to known Bin polyanions the chemical bond in the anion [Bi4]6– is in accordance with the (8‐N) rule featuring solely Bi–Bi single bonds. [Bi4]6– is a butane‐analog valence compound, and with 6 negative charges per 4 atoms it is the anion with the highest known charge per atom obtained from solution. The planarity of the trans‐[Bi4]6– unit hints at π orbital contributions of the bismuth atoms. The corresponding reactions of the phases K5Bi4 and K3Bi2 in liquid ammonia in the presence of [2.2.2]crypt(4, 7, 13, 16, 21, 24‐hexaoxa‐1, 10‐diazabicyclo‐[8.8.8]hexacosane) lead to the salt [K([2.2.2]crypt)]2[Bi2](NH3)4 with the known electron‐deficient [Bi2]2– polyanion and a Bi=Bi double bond.

“My favorite place on earth is Yosemite National Park. The most significant scientific advance of the last 100 years has been the identification of the Higgs Boson …︁” This and more about Jonathan R. Nitschke can be found on page 12928.

The reactivity of TiCp2Cl2 (d0) towards Zintl clusters was studied in liquid ammonia (Cp=cyclopentadienyl). Reduction of TiIVCp2Cl2 and ligand exchange led to the formation of [TiIIICp2(NH3)2]+, also obtainable by recrystallization of [CpTiIIICl]2. Upon reaction with [K4Sn9], ligand exchange leads to [TiCp2(η1‐Sn9)(NH3)]3−. A small variation of the stoichiometry led to the formation of [Ti(η4‐Sn8)Cp]3−, which cocrystallizes with [TiCp2(NH3)2]+ and [TiCp2(η1‐Sn9)(NH3)]3−. Finally, the large intermetalloid cluster anion [Ti4Sn15Cp5]n− (n=4 or 5) was obtained from the reaction of K12Sn17 and TiCp2Cl2 in liquid ammonia. The isolation of three side products, [K([18]crown‐6)]Cp, [K([18]crown‐6)]Cp(NH3), and [K([2.2]crypt)]Cp, suggests a stepwise elimination of the Cl− and Cp− ligands from TiCp2Cl2 and thus gives a hint to the mechanism of the product formation in which [Ti(η4+2‐Sn8)Cp]3− has a key role.

The MgBr2‐catalyzed formal [3+2] cycloaddition of donor–acceptor activated cyclopropanes with nitrosoarenes offers a novel approach to various structurally diverse isoxazolidines. The reactions, which are experimentally easy to conduct, occur with complete stereospecificity and perfect control of regioselectivity. Product isoxazolidines can be readily transformed into α‐amino lactones by reductive or decarboxylative NO cleavage and subsequent lactonisation, and the N‐aryl bond cleavage is also possible under oxidative conditions.

The introduction of a mesityl (Mes; 2,4,6‐Me3C6H2) ligand to a Ge9 polyanion is accomplished by the reaction of [Ge9]4– solutions with Ag4Mes4. The crystal structure investigation of its [K([2.2.2]crypt)] salt ([2.2.2]crypt: 4,7,13,16,21,24‐hexaoxa‐1,10‐diazabicyclo[8.8.8]hexacosane) shows that [Ge9Mes]3– comprises one exo‐bonded aryl ligand in accordance with the 1H NMR spectroscopic data. The formation of mono‐, bis‐, and tris‐substituted Zintl Ions [Ge9Rn](4–n)– (n = 1, 2, and 3; R = CHCH2) is investigated by 1H NMR spectroscopy. The mono‐ and bis‐vinylated Ge9 clusters, [Ge9(CHCH2)]3– and [Ge9(CHCH2)2]2–, were obtained by the reaction of K4Ge9 with Me3SiC≡CSiMe3 in ethylenediamine. In the presence of [18]crown‐6 (1,4,7,10,13,16‐hexaoxacyclooctadecane) and K(C5H5) crystals containing both cluster species were isolated and structurally characterized as[K([18]crown‐6)]2{(η5‐C5H5)[K([18]crown‐6)]2}[Ge9(CHCH2)]and [K([18]crown‐6)]{(η5‐C5H5)[K([18]crown‐6)]2}[Ge9(CHCH2)2], respectively. 1H NMR experiments hint for the tris‐vinylated cluster [Ge9(CHCH2)3]–.