Self‐organized Ruthenium–Barium Core–Shell Nanoparticles on a Mesoporous Calcium Amide Matrix for Efficient Low‐Temperature Ammonia Synthesis

A low‐temperature ammonia synthesis process is required for on‐site synthesis. Barium‐doped calcium amide (Ba‐Ca(NH₂)₂) enhances the efficacy of ammonia synthesis mediated by Ru and Co by 2 orders of magnitude more than that of a conventional Ru catalyst at temperatures below 300 °C. Furthermore, the presented catalysts are superior to the wüstite‐based Fe catalyst, which is known as a highly active industrial catalyst at low temperatures and pressures. Nanosized Ru–Ba core–shell structures are self‐organized on the Ba‐Ca(NH₂)₂ support during H₂ pretreatment, and the support material is simultaneously converted into a mesoporous structure with a high surface area (>100 m² g⁻¹). These self‐organized nanostructures account for the high catalytic performance in low‐temperature ammonia synthesis.     

Experimente mit Erdalkalimetallen

Reactions of the alkaline earth metals magnesium, calcium, strontium, and barium with water, phenolphthalein solution, diluted extract of red cabbage, diluted hydrochloric acid, or ammonia are well suited for a demonstration of the increase in reactivity within this group of metals with increasing atomic number. If the alkali metals lithium and sodium are included, the reactivity of six s‐block elements can be demonstrated in test tubes with small amounts of chemicals.     

Nucleophilic Aromatic Substitution at Benzene with Powerful Strontium Hydride and Alkyl Complexes

Key to the isolation of the first alkyl strontium complex was the synthesis of a strontium hydride complex that is stable towards ligand exchange reactions. This goal was achieved by using the super bulky β‐diketiminate ligand ^DIPePBDI (CH[C(Me)N‐DIPeP]₂, DIPeP=2,6‐diisopentylphenyl). Reaction of ^DIPePBDI‐H with Sr[N(SiMe₃)₂]₂ gave (^DIPePBDI)SrN(SiMe₃)₂, which was converted with PhSiH₃ into [(^DIPePBDI)SrH]₂. Dissolved in C₆D₆, the strontium hydride complex is stable up to 70 °C. At 60 °C, H–D isotope exchange gave full conversion into [(^DIPePBDI)SrD]₂ and C₆D₅H. Since H–D exchange with D₂ is facile, the strontium hydride complex served as a catalyst for the deuteration of C₆H₆ by D₂. Reaction of [(^DIPePBDI)SrH]₂ with ethylene gave [(^DIPePBDI)SrEt]₂. The high reactivity of this alkyl strontium complex is demonstrated by facile ethylene polymerization and nucleophilic aromatic substitution with C₆D₆, giving alkylated aromatic products and [(^DIPePBDI)SrD]₂.     

Transition‐Metal Chemistry of Alkaline‐Earth Elements: The Trisbenzene Complexes M(Bz)3 (M=Sr,Ba)

We report the synthesis and spectroscopic identification of the trisbenzene complexes of strontium and barium M(Bz)₃ (M=Sr, Ba) in low‐temperature Ne matrix. Both complexes are characterized by a D₃ symmetric structure involving three equivalent η⁶‐bound benzene ligands and a closed‐shell singlet electronic ground state. The analysis of the electronic structure shows that the complexes exhibit metal–ligand bonds that are typical for transition metal compounds. The chemical bonds can be explained in terms of weak donation from the π MOs of benzene ligands into the vacant (n?1)d AOs of M and strong backdonation from the occupied (n?1)d AO of M into vacant π* MOs of benzene ligands. The metals in these 20‐electron complexes have 18 effective valence electrons, and, thus, fulfill the 18‐electron rule if only the metal–ligand bonding electrons are counted. The results suggest that the heavier alkaline earth atoms exhibit the full bonding scenario of transition metals.