Zintl ions in molecular compounds are of fundamental interest for basic research and application. Two reactive antimony sources are presented that allow direct access to molecular polystibide compounds. These are Sb amalgam (Sb/Hg) and ultrasmall Sb nanoparticles (d=6.6±0.8 nm), which were used independently as precursors for the synthesis of the largest f-element polystibide, [(Cp* Sm) Sb ]. Whereas the reaction of the nanoparticles with [Cp* Sm] directly led to [(Cp* Sm) Sb ], Sm/Sb/Hg intermediates were isolated when using Sb/Hg as the precursor. These Sm/Sb/Hg intermediates [{(Cp* Sm) Sb} (μ-Hg)] and [{(Cp* Sm) (μ ,η -Sb )} Hg] were synthetically trapped and structurally characterized, giving insight in the formation mechanism of polystibide compounds.

Zintl phases of arsenic and molecular compounds containing Zintl‐type polyarsenide ions are of fundamental interest in basic and applied sciences. Unfortunately, the most obvious and reactive arsenic source for the preparation of defined molecular polyarsenide compounds, yellow arsenic As4, is very inconvenient to prepare and neither storable in pure form nor easy to handle. Herein, we present the synthesis and reactivity of elemental As0 nanoparticles (As0Nano, d=7.2±1.8 nm), which were successfully utilized as a reactive arsenic source in reductive f‐element chemistry. Starting from [Cp*2Sm] (Cp*=η5‐C5Me5), the samarium polyarsenide complexes [(Cp*2Sm)2(μ‐η2:η2‐As2)] and [(Cp*2Sm)4As8] were obtained from As0nano, thereby generating the largest molecular polyarsenide of the f‐elements and circumventing the use of As4 in preparative chemistry.

Bimetallic NiIr4 and NiOs4 alloy nanoparticles are prepared and studied with regard to their performance in catalytic hydrogenation reactions. NiIr4 and NiOs4 nanoparticles are obtained by oleylamine‐driven reduction and exhibit mean diameters of (8.9±1.3) and (6.8±1.4) nm at low agglomeration. The phase composition was determined in detail by using different methods, which include high‐resolution TEM, scanning transmission electron microscopy, selected‐area electron diffraction, X‐ray diffraction, and energy‐dispersive X‐ray spectroscopy. This and results in a uniform distribution of both metals Ni‐Ir and Ni‐Os with a ratio of 1:4. The catalytic performance of the NiIr4 and NiOs4 nanoparticles for hydrogenation reactions is evaluated using three selected model substrates: 1‐octene, cinnamaldehyde, and diphenylacetylene. Similar sized Ni, Ir, and Os nanoparticles were used as references. Most remarkable are the excellent selectivity of NiOs4 in the hydrogenation of cinnamaldehyde and the promising formation of (Z)‐stilbene in terms of conversion activity and selectivity. The alloying of Ir and Os with Ni, moreover, is highly cost efficient. In general, both bimetallic alloy nanoparticles, NiIr4 and NiOs4, are shown here for the first time in terms of synthesis, composition, and catalytic hydrogenation.

CoN, Ni3N and Cu3N nanoparticles were obtained by pyridine-based synthesis using CoI2, NiI2, and CuI as the starting materials as well as NH3/KNH2 as the base and nitride source. Colloidally stable suspensions of crystalline, small-sized CoN (4.5 ± 0.7 nm), Ni3N (2.7 ± 0.4 nm), and Cu3N (4.2 ± 0.7 nm) were instantaneously available from refluxing pyridine. This approach strictly avoids all oxygen sources (including starting materials and solvents), which is highly relevant with regard to the material purity and properties.