Inorganics, Volume 10, Issue 2 (February 2022) – 12 articles

This study combined density functional theory (DFT) calculations and multivariate linear regression (MLR) to analyze the monomer poisoning effect in ethylene/polar monomer copolymerization catalyzed by the Brookhart-type catalysts. The calculation results showed that the poisoning effect of polar monomers with relatively electron-deficient functional groups is weaker, such as ethers, and halogens. On the contrary, polar monomers with electron-rich functional groups (carbonyl, carboxyl, and acyl groups) exert a stronger poisoning effect. In addition, three descriptors that significantly affect the poisoning effect have been proposed on the basis of the multiple linear regression model, viz., the chemical shift of the vinyl carbon atom and heteroatom of polar monomer as well as the metal-X distance in the σ-coordination structure. It is expected that these models could guide the development of efficient catalytic copolymerization system in this field. Full article

Reactivity studies of the classical divalent lanthanide compound [Cp^Bz5₂Sm] (Cp^Bz5 = pentabenzylcyclopentadienyl-anion) towards diphenyl dichalcogenides and d-element carbonyl complexes led to remarkable results. In the compounds obtained, a different number of Sm-C(phenyl) interactions and differently oriented benzyl groups were observed, suggesting—despite the preference of these interactions in [Cp^Bz5₂Sm] described in previous studies—a flexible orientation of the benzyl groups and thus a variable steric shielding of the metal center by the ligand. The obtained compounds are either present as monometallic complexes (reduction of the dichalcogenides) or tetrametallic bridged compounds in the case of the d/f-element carbonyl complexes. Full article

In eukaryotic photosynthetic organisms, ferredoxin–thioredoxin reductases (FTRs) are key proteins reducing several types of chloroplastic thioredoxins (TRXs) in light conditions. The electron cascade necessary to reduce oxidized TRXs involves a pair of catalytic cysteines and a [4Fe–4S] cluster present at the level of the FTR catalytic subunit, the iron–sulfur cluster receiving electrons from ferredoxins. Genomic analyses revealed the existence of FTR orthologs in non-photosynthetic organisms, including bacteria and archaea, referred to as ferredoxin-disulfide reductase (FDR) as they reduce various types of redoxins. In this study, we describe the tridimensional structure of a natural hybrid protein formed by an N-terminal glutaredoxin-like domain fused to a FDR domain present in the marine bacterium Desulfotalea psychrophila Lsv54. This structure provides information on how and why the absence of the variable subunit present in FTR heterodimer which normally protects the Fe–S cluster is dispensable in FDR proteins. In addition, modelling of a tripartite complex based on the existing structure of a rubredoxin (RBX)–FDR fusion present in anaerobic methanogen archaea allows recapitulating the electron flow involving these RBX, FDR and GRX protein domains. Full article

For several decades, coumarins have attracted considerable attention due to the fact of their application in diverse fields such as medical science and biomedical research as well as several industrial branches. Recently, many compounds containing the coumarin moiety have been intensively studied, mainly due to the fact of their biological activities such as antitumor, antioxidative, anti-HIV, vasorelaxant, antimicrobial, and anticancer. They are also widely used as fluorescent dyes and probes because of their great structural flexibility and large fluorescent quantum yields. For this reason, numerous attempts have been made to develop new and more practical methods for the synthesis of these compounds. This review aims at providing a comprehensive overview of coumarin synthesis methods by direct C–H bond activation in order to demonstrate the current state-of-the-art methods as well as the current limitations. Full article

The reactions of pyrazole derivative, i.e., ethyl-5-amino-1-methyl-1H-pyrazole-4-carboxylate (L) with zinc halogenides in methanolic solution and zinc nitrate and zinc acetate in acetonic solution are described. The formulae of synthesized compounds are ZnL₂Cl₂ (1), [ZnL₂Br₂] (2), ZnL₂I₂·0.5MeOH (3), [Zn(L)₂(H₂O)₄](NO₃)₂ (4), and {ZnL(OAc)₂}₂ (5). Two complexes are obtained in form of single crystals: [ZnL₂Br₂] (2) and [Zn(L)₂(H₂O)₄](NO₃)₂ (4). Their crystal and molecular structure were determined by single-crystal X-ray structure analysis. The FTIR spectra of compounds prove the complex formation with all five zinc salts. The complexes are characterized by conductometric and thermoanalytical measurements, and their antioxidative activity was also tested by the scavenging effect on the DPPH radical. Conductometric results, solvolytic stability, and antioxidative activity of the compounds are in correlation. Full article

The monothiocarbonate ligand, [S(O)COR]⁻, is unusual and rare regarding its use in the formation of coordination compounds. Here, we report the synthesis and structures of the silver(I) and gold(I) monothiocarbonate complexes, [{Ag₄(SC(O)OⁱPr)₂(2,2′-bpy)₄}(PF₆)₂]_n (1) and [Au₂{S(O)COⁱPr}₂(dppe)]_n (2), respectively. Both complexes are coordination polymers, with 1 being cationic and 2 neutral. The uniqueness of the ligand is that it is monoanionic and contains both a ‘hard’ O-donor ligand and a ‘soft’ S-donor ligand in a O-C-S manifold with, in principle, electron delocalization across the three atoms. However, for both complexes 1 and 2, it was found that the binding occurred exclusively through the S-donor atom, while the C=O portion remained dangling and was not involved in bonding. This bonding mode departs significantly from the symmetrical S-C-S type ligand such as dithiocarbamates. The structures were analysed and confirmed by NMR and X-ray crystallography. Full article

We synthesized and structurally characterized the previously unknown [Co(NH₃)₅Cl](MnO₄)₂ complex as the precursor of CoMn₂O₄. The complex was also deuterated, and its FT-IR, far-IR, low-temperature Raman and UV-VIS spectra were measured as well. The structure of the complex was solved by single-crystal X-ray diffraction and the 3D-hydrogen bonds were evaluated. The N-H…O-Mn hydrogen bonds act as redox centers to initiate a solid-phase quasi-intramolecular redox reaction even at 120 °C involving the Co(III) centers. The product is an amorphous material, which transforms into [Co(NH₃)₅Cl]Cl₂, NH₄NO₃, and a todorokite-like solid Co-Mn oxide on treatment with water. The insoluble residue may contain {Mn₄^IIIMn^IV₂O₁₂}_n⁴ⁿ⁻, {Mn₅^IIIMn^IVO₁₂}_n⁵ⁿ⁻ or {Mn^III₆O₁₂}_n⁶ⁿ⁻ frameworks, which can embed 2 × n (Co^II and/or Co^III) cations in their tunnels, respectively, and 4 × n ammonia ligands are coordinated to the cobalt cations. The decomposition intermediates decompose on further heating via a series of redox reactions, forming a solid Co^IIM^III₂O₄ spinel with an average size of 16.8 nm, and gaseous N₂, N₂O and Cl₂. The CoMn₂O₄ prepared in this reaction has photocatalytic activity in Congo red degradation with UV light. Its activity strongly depends on the synthesis conditions, e.g., Congo red was degraded 9 and 13 times faster in the presence of CoMn₂O₄ prepared at 550 °C (in air) or 420 °C (under N₂), respectively. Full article

Phosphinines and donor-substituted phosphinines are of recent interest due to their use in homogeneous catalysis. In this article, a Pd(II) bis(phosphinine) complex was characterised and phosphorus–selenium coupling constants were used to assess the donor properties of the diphenylphosphine substituents of phosphinine ligands to promote their further use in catalysis. The selenation of 2,5-bis(diphenylphosphino)-3,6-dimethylphosphinine (5) and 2-diphenylphosphino-3-methyl-6-trimethylsilylphosphinine (6) gave the corresponding phosphine selenides 8 and 9, respectively, leaving the phosphinine ring intact. Multinuclear NMR spectroscopy, mass spectrometry and single crystal X-ray diffraction confirmed the oxidation of all the diphenylphosphine substituents with ¹J_P-Se coupling constants determined to be similar to SePPh₃, indicating that the phosphinine rings were electronically similar to phenyl substituents. Solutions of 6 were found to react with oxygen slowly to produce the phosphine oxide 10 along with other by-products. The reaction of [bis{3-methyl-6-(trimethylsilyl)phosphinine-2-yl}dimethylsilane] (4) with [PdCl₂(COD)] gave the chelating dichloropalladium(II) complex, as determined by multinuclear NMR spectroscopy, mass spectrometry and an elemental analysis. The molecular structure of the intermediate 2 in the formation of 4,6-di(tert-butyl)-1,3,2-diazaphosphinine (3) was also determined, which confirmed the structure of the diazaphosphacycle P(Cl){N=C(^tBu)CH=C(^tBu)-N(H)}. Full article

Zinc nitrate (ZnO_N) and zinc acetate (ZnO_A) were used as precursors for the synthesis of zinc oxide (ZnO) nanoparticles by the sol–gel method. The ZnO powder was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV–vis diffuse reflectance spectroscopy, X-ray diffraction (UV–Vis DRS), Fourier transform infrared spectroscopy (FTIR), physisorption of nitrogen, and X-ray photoelectron spectroscopy (XPS). On the other hand, the photocatalytic activity of the samples was tested in the degradation of 2,4-Dichlorophenoxyacetic acid (2,4-D) and 2,4-Dichlorophenol (2,4-DCP) under UV-light irradiation. The ZnO_N and ZnO_A showed polycrystalline irregular structures and rod-like morphology with mean sizes of 40 and 99 nm, respectively. The precursor type influenced the bandgap, crystallite size, surface area, total pore volume, and pore diameter. The XPS results showed high contents of C and N in the ZnO samples, and as a consequence, the solids present remarkable differences in the C/N, O/C, and O/Zn atomic ratios, which significantly influenced the physicochemical characteristics. The ZnO_N and ZnO_A exhibit photocatalytic properties against 2,4-D (74.7 and 90.9%, respectively) and 2,4-DCP (78.4 and 86.7%, respectively) and better performance of ZnO_A. These results are promising and indicate the potential to use this material as a photocatalyst to degrade organic pesticides. Full article

The development of solvent-free techniques for nanoparticles synthesis is one of the challenges of Green chemistry. In this work, the principled opportunity to obtain copper-containing nanosized particles without use of any solvents was shown. The copper complexes were prepared as precursors by the melting-assisted solvent-free synthesis. The formation of tetra(imidazole)copper(II) nitrate complex was confirmed by XRD, elemental analysis, FTIR spectroscopy, and thermal analysis. It was noted that their thermal decomposition occurs in two stages: (I) the low-temperature step may be related to redox interaction between organic ligands and nitrate-anions; (II) the high-temperature step may be related to the oxidation of the products of incomplete imidazole decomposition. TEM and XRD studies of solid products of complex combustion have shown that they are oxides with particle size less than 40 nm. Thus, the combustion of [Cu(Im)₄](NO₃)₂ complex under air can be considered as a new approach to prepare nanosized particles of copper oxides without the use of solvents. Full article