A General and Highly Selective Palladium‐Catalyzed Hydroamidation of 1,3‐Diynes

A chemo‐, regio‐, and stereoselective mono‐hydroamidation of (un)symmetrical 1,3‐diynes is described. Key for the success of this novel transformation is the utilization of an advanced palladium catalyst system with the specific ligand Neolephos. The synthetic value of this general approach to synthetically useful α‐alkynyl‐α, β‐unsaturated amides is showcased by diversification of several structurally complex molecules and marketed drugs. Control experiments and density‐functional theory (M06L‐SMD) computations also suggest the crucial role of the substrate in controlling the regioselectivity of unsymmetrical 1,3‐diynes.     

Combined Crossed Molecular Beams and Ab Initio Study of the Bimolecular Reaction of Ground State Atomic Silicon (Si; 3P) with Germane (GeH4; X1A1)

The chemical dynamics of the elementary reaction of ground state atomic silicon (Si; ³P) with germane (GeH₄; X¹A₁) were unraveled in the gas phase under single collision condition at a collision energy of 11.8±0.3 kJ mol⁻¹ exploiting the crossed molecular beams technique contemplated with electronic structure calculations. The reaction follows indirect scattering dynamics and is initiated through an initial barrierless insertion of the silicon atom into one of the four chemically equivalent germanium-hydrogen bonds forming a triplet collision complex (HSiGeH₃; ³ i1 ). This intermediate underwent facile intersystem crossing (ISC) to the singlet surface (HSiGeH₃; ¹ i1 ). The latter isomerized via at least three hydrogen atom migrations involving exotic, hydrogen bridged reaction intermediates eventually leading to the H₃SiGeH isomer i5 . This intermediate could undergo unimolecular decomposition yielding the dibridged butterfly-structured isomer ¹ p1 (Si(μ-H₂)Ge) plus molecular hydrogen through a tight exit transition state. Alternatively, up to two subsequent hydrogen shifts to i6 and i7 , followed by fragmentation of each of these intermediates, could also form ¹ p1 (Si(μ-H₂)Ge) along with molecular hydrogen. The overall non-adiabatic reaction dynamics provide evidence on the existence of exotic dinuclear hydrides of main group XIV elements, whose carbon analog structures do not exist.     

Application of Natural Clinoptilolite for Ammonium Removal from Sludge Water

Sludge water (SW) arising from the dewatering of anaerobic digested sludge causes high back loads of ammonium, leading to high stress (inhibition of the activity of microorganisms by an oversupply of nitrogen compounds (substrate inhibition)) for wastewater treatment plants (WWTP). On the other hand, ammonium is a valuable resource to substitute ammonia from the energy intensive Haber-Bosch process for fertilizer production. Within this work, it was investigated to what extent and under which conditions Carpathian clinoptilolite powder (CCP 20) can be used to remove ammonium from SW and to recover it. Two different SW, originating from municipal WWTPs were investigated (SW1: c₀ = 967 mg/L NH₄-N, municipal wastewater; SW2: c₀ = 718–927 mg/L NH₄-N, large industrial wastewater share). The highest loading was achieved at 307 K with 16.1 mg/g (SW1) and 15.3 mg/g (SW2) at 295 K. Kinetic studies with different specific dosages (0.05 g_CLI/mg_NH4-N), temperatures (283–307 K) and pre-loaded CCP 20 (0–11.4 mg/g) were conducted. At a higher temperature a higher load was achieved. Already after 30 min contact time, regardless of the sludge water, a high load up to 7.15 mg/g at 307 K was reached, achieving equilibrium after 120 min. Pre-loaded sorbent could be further loaded with ammonium when it was recontacted with the SW.     

Self-propelled droplets

Self-propelled droplets are a special kind of self-propelled matter that are easily fabricated by standard microfluidic tools and locomote for a certain time without external sources of energy. The typical driving mechanism is a Marangoni flow due to gradients in the interfacial energy on the droplet interface. In this article we review the hydrodynamic prerequisites for self-sustained locomotion and present two examples to realize those conditions for emulsion droplets, i.e. droplets stabilized by a surfactant layer in a surrounding immiscible liquid. One possibility to achieve self-propelled motion relies on chemical reactions affecting the surface active properties of the surfactant molecules. The other relies on micellar solubilization of the droplet phase into the surrounding liquid phase. Remarkable cruising ranges can be achieved in both cases and the relative insensitivity to their own ‘exhausts’ allows to additionally study collective phenomena.     

Zero-temperature magnetic transition in an easy-axis Kondo lattice model

We address the quantum transition of a spin-1/2 antiferromagnetic Kondo lattice model with an easy-axis anisotropy using the extended dynamical mean field theory. We derive results in real frequency by using the bosonic numerical renormalization group (BNRG) method and compare them with quantum Monte Carlo results in Matsubara frequency. The BNRG results show a logarithmic divergence in the critical local spin susceptibility, signaling a destruction of Kondo screening. The T=0 transition is consistent with being second order. The BNRG results also display some subtle features; we identify their origin and suggest means for further microscopic studies.     

Click Chemistry in Ultra-high Vacuum – Tetrazine Coupling with Methyl Enol Ether Covalently Linked to Si(001)

The additive-free tetrazine/enol ether click reaction was performed in ultra-high vacuum (UHV) with an enol ether group covalently linked to a silicon surface: Dimethyl 1,2,4,5-tetrazine-3,6-dicarboxylate molecules were coupled to the enol ether group of a functionalized cyclooctyne which was adsorbed on the silicon (001) surface via the strained triple bond of cyclooctyne. The reaction was observed at a substrate temperature of 380 K by means of X-ray photoelectron spectroscopy (XPS). A moderate energy barrier was deduced for this click reaction in vacuum by means of density functional theory based calculations, in good agreement with the experimental results. This UHV-compatible click reaction thus opens a new, flexible route for synthesizing covalently bound organic architectures.     

Enantiopure Calcium Iminophosphonamide Complexes: Synthesis,Photoluminescence, and Catalysis

The synthesis of calcium complexes ligated by three different chiral iminophosphonamide ligands, L- H ( L =[Ph₂P{N(R)CH(CH₃)Ph}₂]), L′ -H ( L′ =[Ph₂P{NDipp}{N(R)CH(CH₃)Ph}]), (Dipp=2,6-ⁱPr₂C₆H₃), and L′′ -H ( L′′ =[Ph₂P{N(R)CH(CH₃)naph}₂]), (naph=naphthyl) is presented. The resulting structures [ L ₂Ca], [ L′ ₂Ca], and [ L′′ ₂Ca] represent the first examples of enantiopure homoleptic calcium complexes based on this type of ligands. The calcium complexes show blue–green photoluminescence (PL) in the solid state, which is especially bright at low temperatures. Whereas the emission of [ L′′ ₂Ca] is assigned to the fluorescence of naphthyl groups, the PL of [ L ₂Ca] and [ L′ ₂Ca] is contributed by long-lived phosphorescence and thermally activated delayed fluorescence (TADF), with a strong variation of the PL lifetimes over the temperature range of 5–295 K. Furthermore, an excellent catalytic activity was found for these complexes in hydroboration of ketones at room temperature, although no enantioselectivity was achieved.     

Application of the Redox-Transmetalation Procedure to Access Divalent Lanthanide and Alkaline-Earth NHC Complexes**

Divalent lanthanide and alkaline-earth complexes supported by N-heterocyclic carbene (NHC) ligands have been accessed by redox-transmetalation between air-stable NHC-AgI complexes and the corresponding metals. By using the small ligand 1,3-dimethylimidazol-2-ylidene (IMe), two series of isostructural complexes were obtained: the tetra-NHC complexes [LnI₂(IMe)₄] (Ln=Eu and Sm) and the bis-NHC complexes [MI₂(IMe)₂(THF)₂] (M=Yb, Ca and Sr). In the former, distortions in the NHC coordination were found to originate from intermolecular repulsions in the solid state. Application of the redox-transmetalation strategy with the bulkier 1,3-dimesitylimidazol-2-ylidene (IMes) ligand yielded [SrI₂(IMes)(THF)₃], while using a similar procedure with Ca metal led to [CaI₂(THF)₄] and uncoordinated IMes. DFT calculations were performed to rationalise the selective formation of the bis-NHC adduct in [SrI₂(IMe)₂(THF)₂] and the tetra-NHC adduct in [SmI₂(IMe)₄]. Since the results in the gas phase point towards preferential formation of the tetra-NHC complexes for both metal centres, the differences between both arrangements are a result of solid-state effects such as slightly different packing forces.     

Influence of higher harmonics of the undulator in X‐ray polarimetry and crystal monochromator design

The spectrum of the undulator radiation of beamline P01 at Petra III has been measured after passing a multiple reflection channel‐cut polarimeter. Odd and even harmonics up to the 15th order, as well as Compton peaks which were produced by the high harmonics in the spectrum, could been measured. These additional contributions can have a tremendous influence on the performance of the polarimeter and have to be taken into account for further polarimeter designs.