European Journal of Inorganic Chemistry最新文献

The Front Cover shows new linear and cyclo-hexaboranes. Their structures were confirmed by X-ray diffraction of single crystal analysis. The B−B bonds in the linear hexaborane are twisted, and the cyclo-hexaborane has a chair conformation similar to that of cyclohexane. These rare crystal structures of B₆ chain and B₆ ring polyboranes can be likened to valuable pieces of jewelry. More information can be found in the Research Article by A. W. Mesbah and co-workers.

The Front Cover illustrates the preparation of novel lithium zincate alkoxo clusters, achieved through a co-complexation reaction between dialkylzinc derivatives and lithium alkoxides. The image features a cartoon-like green figure with “Zn” on its head, representing diethylzinc. Zn is equipped with robotic arms labeled “C” for carbon, symbolizing its attempt to manipulate and break the lithium alkoxide cage by using a scalpel, which serves as a metaphor for the pivotal role of diethylzinc in the reaction. More details can be found in the Research Article by E. Hevia, V. Capriati and co-workers.

The Front Cover shows four groups of children in an aluminum playground. Each group symbolizes a different type of aluminum structure, with variations in the ligand substituents. Each child represents an aluminum center, with their color-coded jackets and hats signifying the distinct coordination environments of the metal. Additionally, the four groups feature captions highlighting their most notable properties, including the ability to perform ring-opening polymerization of ϵ-caprolactone. More information can be found in the Research Article by U. Hernández-Balderas, M. Moya-Cabrera and co-workers.

The Cover Feature illustrates the uneven fight between our gaseous hero Gas-Face (“He He He”) and the evil PP-Pig-Man “coordinating” cationic Pt^II-thiomethoxymethyl complexes. By virtue of Gas-Face′s superpower—to be everywhere—collisions of the (PP-Pig-Man-)diphospine complexes with helium cause their gas-phase fragmentation. Depending on the bite angle, different neutrals are lost: while neutral dimethylsulfide is preferentially ejected for bite angles >90° (here dPPb), the loss of ethene and thioformaldehyde dominates for bite angles <90° (here dPPm). More information can be found in the Research Article by B. Butschke and co-workers.

The Front Cover indicates the conversion of waste into a resource. The letters make up the word “FAMEs”, which is the chemical description of biodiesel. Each letter occupies its own quadrant, describing the process with an image: waste cooking oil (F) was converted by using waste steel slags (A) as the catalyst, due to their alkaline features (M), under microwave irradiation (Es), thus preserving the environment. More information can be found in the Research Article by M. M. Dell'Anna, P. Mastrorilli and co-workers.

Organophosphate compounds (OPC) are chemical species with a broad range of applications from agricultural to medicinal chemistry, which however rose sadly to the fore for their use as chemical weapons worldwide. Several efforts are therefore carried out to contrast their toxic effects or to repurpose OPC for chemical synthesis. In this regard, metal-containing systems, like metal-organic frameworks or complexes, represent a valid solution for the treatments of OPC in a number of fields. Our work has been inspired by the recent findings concerning the reactivity of (^iPrPN^HP)Mn(CO)₂(OH) (1) complex with P−F bond containing organophosphate compounds. We, in particular, have investigated three different OPC, which are diisopropylfluorophosphate (a), isopropylfluorophosphoric acid (b) and fluorophosphoric acid (c), extending the complex 1 reactivity to the nerve gas sarin (sa). The reaction concerns the leaving of fluoride from OPC, to produce relative defluorinated phosphates and the (^iPrPN^HP)Mn(CO)₂(F) complex. Analysis of the calculations revealed that the reaction is favored from both thermodynamic and kinetical points of view for a substrate. Our results are in agreement with the available experimental data and represent a further confirmation of versatility of such metal-complex to interact with P−F containing toxic agents.

We present co-crystallization as an approach to tuning spin crossover (SCO) properties of mononuclear Mn(III) Schiff-base complexes. Complexes [Mn(5-F-sal-N-1,5,8,12)]ClO₄ ⋅ 0.5carbazole (cocrystal 1 a) and [Mn(5-F-sal-N-1,5,8,12)]PF₆ ⋅ 0.5carbazole (cocrystal 2 b) are synthesized by the co-crystallization of their parent complexes ( [Mn(5-F-sal-N-1,5,8,12)]Y, Y=ClO₄⁻ (1); Y=PF₆⁻ (2) ) with the carbazole and they both exhibit HS electronic configurations between 2 and 300 K. While, the parent complex 1 shows a nearly complete SCO with T_1/2=100 K and complex 2 maintains a high-spin (HS) state. The introduction of carbazole as the third component has a great influence on cation-anion crystal packing and finally the cooperative effects of the SCO complexes.

An innovative catalytic system for biodiesel synthesis starting from waste biomass (waste cooking oil, WCO) in the presence of waste material (steel slags) as the catalyst under microwave irradiation is described. The reaction conditions were optimized by using response surface methodology (RSM) based on Box-Behnken Design (BBD) taking time, temperature, and catalyst weight as factors. The optimum conditions, leading to 97 % conversion of WCO into FAMEs (fatty acid methyl esters) were found to be: 18 min reaction time, 134 °C and 380 mg of catalyst for 1.0 mL of WCO. The recyclability of the catalyst was tested at different experimental conditions, and by increasing the reaction times for subsequent cycles, the catalytic efficiency remained steady. The alkalinity of both as-received steel slags and steel slags recovered after three reaction cycles was tested with the Hammett indicator method. The steel slags were also characterized by Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Fluorescence (ED-XRF), X-Ray Diffraction (XRD), Thermogravimetric Analysis (TGA), X-ray Photoelectron Spectroscopy (XPS).

The Front Cover shows a gull on a beautiful sunset flying with a series of smaller cartoonish gulls. In between these gulls, the ingredients for a novel reductive transmetalation route are provided: “AlCp*” and ZnR₂ (R=aryl), which selectively react to yield compounds of the generic formula [AlCp*R₂]. As an example, a crystal structure is shown that spreads its newly introduced aryl rings as wings to fly with the big gull. Corroborated by quantum chemical calculations, such compounds found application for selective CO₂ insertion in their AlCp* moieties to yield small inorganic rings. More information can be found in the Research Article by E. Hevia and F. M. Dankert.

The exceptional reactivity observed in non-heme iron enzymes can be attributed to their capability to access high-valent iron oxygen species in their active site. Numerous inorganic model complexes have been reported to date, providing insights into the intricate structural and spectroscopic features of many iron-containing enzymes and advancing our understanding of their enzymatic reaction pathways. While the reactivities of synthetic iron complexes have been evaluated using various oxidants, the investigation into the formation of reactive intermediates has primarily focused on acetonitrile. However, water, which serves as the medium in biological systems, has been less frequently employed in these studies. Motivated by this, we conducted a comprehensive study on the generation of key reactive species using various oxidants with a model complex, [(BnTPEN)Fe(II)(OTf)]⁺ (1) (where BnTPEN=N-benzyl-N,N,N-tris(2-pyridylmethyl)-1,2-diaminoethane) in water, which yielded important findings. In water, a quantitative yield of Fe(IV)=O species was achieved with the oxidant NaIO₄. Additionally, we observed an equilibrium between side-on Fe(III)−OO and Fe(III)−OOH, with the latter eventually converting to Fe(IV)=O. The insights gained from this study are likely to be relevant in the chemistry of other Fe(II) complexes with polypyridyl pentadentate ligands.