European Journal of Inorganic Chemistry最新文献

Andrea Cingolani, Nicola Schiaroli, Carlo Lucarelli, Chiara Lenzi, Andrea Masetti, Cristiana Cesari, Francesca Forti, Stefano Zacchini, Jacopo De Maron, Francesco Luca Basile, Rita Mazzoni, Eur. J. Inorg. Chem., 2025, 28, e202500203.

In preparing the manuscript, the authors inadvertently missed to reference an earlier work by Knölker et al. that had inspired the synthesis of complex 3 under photolytic conditions. The statement “Upon irradiation at 365 nm of 2 in acetonitrile,” should have been followed by Reference [1].

We apologize for this error.

The isolation of silylene–phosphinidene is challenging due to its rapid dimerization or oligomerization during the reaction. Recently, the synthesis of a novel silylene (1) is reported, which leads to the formation of an unsymmetrical bis-silylene (2), and it's their intriguing reactivity toward silylene(II) is further studied. Expanding on this reactivity, the reaction of 2 with ^MecAACPCl is explored, which affords silylene–phosphinidene [R(MecAAC)SiPCAAc^Me (3)] oxidatively in low yield. Alternatively, when RSiCl(CAAc^Me) (1) is treated with ^MecAACPCl under reducing conditions, compound 3 is obtained in an isolated yield of 78%. In addition, quantum chemical calculations are carried out to elucidate the electronic structures of compounds 3 and 4, providing deeper insight into the nature of their chemical bonding.

A detailed computational study is performed on the structural and spectroscopic properties of R₃PAuCl (R = H, Me, Et) compounds, combining density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations. The investigation addresses the conformational behavior of monomeric and dimeric species in the gas phase and in solution using the conductor-like screening model (COSMO). Dispersion-corrected optimizations reveal that molecular aggregation significantly influences geometry and spectral response. Energy decomposition analysis is employed to quantify the nature of the noncovalent interactions stabilizing the dimeric arrangements. Simulated ultraviolet–visible (UV–vis) spectra, including both radiative and nonradiative transitions, are computed with and without spin-orbit coupling (SOC), highlighting its impact on spectral intensity and agreement with experiment. Solvatochromic trends are analyzed across solvents (toluene, tetrahydrofuran, acetonitrile, and dimethyl sulfoxide), showing that excited-state dipole moments play a central role in the observed shifts. A saturation effect in the solvent response is identified, suggesting limitations of the implicit solvation model at high polarity. The combined results provide a coherent framework to interpret the structural and photophysical properties of these systems and emphasize the relevance of accounting for aggregation state (monomer or dimer), dispersion, SOC, and solvent effects to achieve quantitative agreement with experimental UV–vis spectra.

The Front Cover describes the cyclic organic selenium imides and acyclic imidoselenium chlorides that have been isolated and identified upon cyclocondensation of SeCl₂ and tBuNH₂. The name selenium is derived from selene, the Greek name for the Moon. In their Research Article (DOI: 10.1002/ejic.202500292), H. M. Tuononen, R. S. Laitinen and co-workers present detailed DFT calculations that describe the complicated reaction route in terms of elementary steps involving key intermediate formation, chain extension, and ring closure, in a similar manner to what has been proposed for the formation of cyclophosphazanes and -phosphazenes. Some steps also involve redox processes.

Low-temperature crystal structures of iron carbonyl complexes of diamagnetic 4-aryl-3H-1,2,3,5-dithiadiazolines, [Fe₂{S₂N(NH)CAr}(CO)₆] (Ar = 4-C₆H₄CF₃ (2), and 4-C₆H₄OMe (3)) are reported, alongside a new low-temperature structure of [Fe₂{S₂N(NH)CPh}(CO)₆] (1), in which the presence of an NH bond is established unambiguously. Diverse NH···N hydrogen bonding networks in 1, 2, and several variants of 3 (3a–c) are observed, with intermolecular distances refined to neutron-diffraction accuracy using Hirshfeld atom refinement with nonspherical atomic scattering factors, using a state-of-the-art method. To rationalize the formation of 1–3 from Fe₃(CO)₁₂ and 1,2,3,5-dithiadiazolyl radicals, i.e., the conspicuous absence of paramagnetic [Fe₂(S₂N₂CAr)(CO)₆] (1′–3′), the thermochemistry of the reactions, and properties of viable intermediates are profiled using density functional theory (DFT) methods. From these calculations, a clear electronic basis for the instability of 1′–3′ is revealed: unlike S₂N₂CAr^•, which are stable π radicals, their iron complexes are reactive σ radicals that abstract a hydrogen atom from dry toluene to form the observed diamagnetic complexes. Furthermore, the putative paramagnetic complexes are uniquely susceptible to hydrogen atom transfer and are thus probable intermediates in the syntheses of 1–3.

Complexation modes of bis[(di-tert-butylphosphino)methyl]aminophosphane containing PCPCP structural motif is investigated. The donor ability of each phosphane unit is determined by theoretical calculations and experimentally. Reactions of this ligand with cobalt and iron carbonyl precursors yielded various complexes, with different coordination modes. The three phosphorus donor atoms, connected via methylene bridges, allow for flexible coordination behavior, indeed mono-, di- and tricoordinated complexes are isolated. Single-crystal X-ray diffraction and spectroscopic analysis confirmed the structural diversity of the resulting compounds.

The design and synthesis of cost-effective and environmentally friendly luminescent materials have great implications and challenges. In this study, bulky phosphine ligands (Sphos and Xphos) are utilized to synthesize a series of three-coordinated Cu(I) complexes with different N^N ligands derived from 1,10-phenanthroline. By employing rigid N^N donor ligands featuring different electron-donating or withdrawing substituents, the emission from 585 to 698 nm with a microseconds lifetime in the solid state can be systematically modulated. While complexes 1–3 with 1,10-phenanthroline and neocuproine exhibit emission around 590 nm, dicnq (featuring electron-withdrawing groups) coordinated complexes 4 and 5 exhibit significantly redshifted emissions to ≈700 nm. The experimental and theoretical studies suggest the occurrence of thermally activated delayed fluorescence with microseconds lifetime and a small ΔE_ST. This investigation highlights the pivotal role of ligand design in regulating the photophysical characteristics of Cu(I) complexes.

A. König, C. Fischer¹, E. Alberico², C. Selle, H.-J. Drexler, W. Baumann, D. Heller, Eur. J. Inorg. Chem., 2017, 2040–2047.

Leibniz-Institut für Katalyse e.V., Albert-Einstein-Str. 29A, 18059 Rostock (Germany)

¹Present address: Universität Greifswald, Institut für Biochemie, Felix-Hausdorff-Str. 4, 17487 Greifswald (Germany)

²Permanent address: CNR, Istituto di Chimica Biomoleculare, Traversa La Crucca, 3, 07100 Sassari (Italy)

In Table 1 and the Experimental Section, the chemical shifts δ(¹⁰³Rh) of two rhodium complexes 5b and 6c are given with the inverted sign. The correct data are as follows:

Complex 5b, [Rh(DIPAMP)(Ph)(Br)(MeOH)]BF₄: +1564 ppm (not −1564 ppm)

Complex 6c, [Rh(DIPAMP)(Ph)(I)]₂[BF₄]₂: +1541 ppm (not −1541 ppm)

These shifts are given relative to Ξ(¹⁰³Rh) = 3.16 MHz.

We apologize for this error.

The syntheses and structural characterization of Cu(I)–Rh(I) and Cu(I)–Ir(I) complexes are reported. These complexes are synthesized via the reaction of a previously reported copper amidinate complex, Cu₂L₂ (L= {Ph₂PC≡CC(NDipp)₂}, Dipp = N,N′-2,6-diisopropylphenyl), with [M(cod)Cl]₂, (M= Rh, Ir; cod = 1,5-cyclooctadiene) yielding complexes [{(M(cod)Cl)Ph₂PC≡CC(NDipp)₂}₂Cu₂] (M= Rh, Ir). Additionally, an alternative one-pot synthetic route is explored by the reaction of lithium salt of the ligand, [M(cod)Cl]₂, (M= Rh, Ir), and CuCl, resulting in improved yields of [{(M(cod)Cl)Ph₂PC≡CC(NDipp)₂}₂Cu₂]. Further, reaction of lithium salt of the ligand with [M(cod)Cl]₂, (M= Rh, Ir) leads to the formation of intermediate complexes [{(M(cod)Cl)Ph₂PC≡CC(NDipp)₂}Li(thf)₃] (M= Rh, Ir), which upon hydrolysis, yielded protonated amidinate derivatives [(M(cod)Cl)Ph₂PC≡CC(NDipp)(NHDipp)] (M= Rh, Ir). In the second pathway, lithium salt of the ligand is hydrolyzed to obtain [Ph₂PC≡CC(NDipp)(NHDipp)]₂ and further reaction with [M(cod)Cl]₂, (M= Rh, Ir) yields [(M(cod)Cl)Ph₂PC≡CC(NDipp)(NHDipp)] via an alternative reaction pathway. The catalytic potential of Cu(I)–Ir(I) complex [{(Ir(cod)Cl)Ph₂PC≡CC(NDipp)₂}₂Cu₂] is evaluated for transfer hydrogenation (TH) of aryl aldehydes using isopropanol as a hydrogen transfer source. Furthermore, the Ir complexes [{(Ir(cod)Cl)Ph₂PC≡CC(NDipp)₂}₂Cu₂] and [(Ir(cod)Cl)Ph₂PC≡CC(NDipp)(NHDipp] are found to be luminescent in the solid state at 77 K with an emission maximum around 580 nm.

Metal ions play a key role in regulating antimicrobial peptides (AMPs), either inducing or enhancing their effects against pathogens. In human saliva, AMPs, including fragments of the glycoprotein MUC7, form a natural defense against oral and systemic infections. This study investigates a 20-residue MUC7-derived peptide containing three histidine residues as potential coordination sites for divalent metal ions. Complexes are analyzed using electrospray ionization mass spectrometry, potentiometry, and spectroscopic methods: ultraviolet–visible spectroscopy, circular dichroism, and electron paramagnetic resonance, together with antimicrobial assays. Cu(II) coordination did not significantly alter secondary structure or improve antimicrobial properties. In contrast, Zn(II) induced conformational changes under alkaline conditions, correlating with slightly enhanced antimicrobial performance. Proline, tyrosine, and phenylalanine residues likely modulate metal coordination through steric hindrance and conformational effects. These findings highlight the role of metal coordination in modulating AMP function. Although this particular MUC7-derived fragment exhibits only modest antimicrobial activity compared to other known fragments of this protein, its distinct metal-binding behavior suggests that it may serve an alternative biological role in the oral environment beyond direct pathogen inhibition.