A series of copper(I) halide complexes coordinated by a cyclic thiourea ligand featuring methyl, acetyl, and m-nitrophenyl substituents has been synthesized and structurally elucidated. These complexes were studied using a combination of X-ray single-crystal and powder diffraction, IR, NMR, and UV-vis spectroscopy, alongside DFT calculations. The results revealed a remarkable structural diversity dictated by the halide anion and the solvent used. Copper(I) chloride and bromide form mononuclear complexes with a CuHalL2 composition, while copper(I) iodide forms polynuclear complexes in a 1:1 stoichiometry, exhibiting a unique polymorphism. CuI forms complexes with both polymeric chains and cyclic structures, depending on the solvent used for synthesis and crystallization. DFT calculations were used to characterize the molecular structure and absorption spectra of the complexes. Application of simplified TD-DFT approximation allowed us to assign UV-vis absorbance bands to metal-to-ligand charge transfer (MLCT) transitions. These findings demonstrate a powerful approach to controlling the nuclearity and architecture of copper(I) coordination complexes through variations in anions and crystallization conditions.

Complexes [PdL2Cl2] (I) and [PdL2Вr2] (II) (L is 5-acetyl-6-methyl-4-(3-nitrophenyl)-1,2,3,4-tetrahydropyrimidine-2-thione) are synthesized and characterized by spectral methods (1Н, 13С NMR and IR spectroscopy). The crystal structure of complex I is determined (CIF file ССDС no. 2233053) in which the palladium atom is coordinated by two halide ions and two sulfur atoms of two ligands L in a distorted square planar geometry. The catalytic activity of the synthesized palladium(II) complexes in the model epoxidation of allyl alcohol is estimated in comparison with the catalytic activity of the corresponding palladium halides and titanium-containing zeolite TS-1.

Over the past decades, the problem of bacterial resistance to most antibiotics has become a serious threat to patients’ survival. Nevertheless, antibiotics of a novel class have not been approved since the 1980s. The development of antibiotic potentiators is an appealing alternative to the challenging process of searching for new antimicrobials. Production of H2S—one of the leading defense mechanisms crucial for bacterial survival—can be influenced by the inhibition of relevant enzymes: bacterial cystathionine γ-lyase (bCSE), bacterial cystathionine β-synthase (bCBS), or 3-mercaptopyruvate sulfurtransferase (MST). The first one makes the main contribution to H2S generation. Herein, we present data on the synthesis, in silico analyses, and enzymatic and microbiological assays of novel bCSE inhibitors. Combined molecular docking and molecular dynamics analyses revealed a novel binding mode of these ligands to bCSE. Lead compound 2a manifested strong potentiating activity when applied in combination with some commonly used antibiotics against multidrug-resistant Acinetobacter baumannii, Pseudomonas aeruginosa, and methicillin-resistant Staphylococcus aureus. The compound was found to have favorable in vitro absorption, distribution, metabolism, excretion, and toxicity parameters. The high effectiveness and safety of compound 2a makes it a promising candidate for enhancing the activity of antibiotics against high-priority pathogens.

Министерство науки и высшего образования Российской Федерации Российская академия наук Научный совет по неорганической химии РАН Научный совет по аналитической химии РАН Научный совет по химической технологии РАН Российское химическое общество имени Д.И

The first copper(i) and palladium(ii) complexes containing monastrol analogs, 4-thioxo[1,3,5]oxadiazocine derivatives, have been synthesized. The complexes demonstrated significant antibacterial activity in contrast to free heterocyclic thiones.

The generation of carbon-centered radicals from air-sensitive organoboron compounds via nucleohomolytic substitution at boron is one of the most general methods to generate non-functionalized and functionalized radicals. Due to their reduced Lewis acidity, the very popular, air-stable, and readily available alkylboronic pinacol esters are not suitable substrates for this process. Herein, is reported their in situ conversion to alkylboronic catechol esters by boron-transesterification with a substoichiometric amount of catechol methyl borate (MeO–Bcat) telescoped onto a wide array of radical chain processes. This simple one-pot, radical-chain, deboronative protocol allows for the conversion of pinacol boronic esters into iodides, bromides, chlorides, and thioethers. The process is also suitable the formation of nitriles and allylated compounds via C–C bond formation using sulfonyl radical traps. Finally, a particularly mild protocol for the protodeboronation of pinacol boronic esters is given. The power of combining radical and classical boron chemistry, is illustrated with a highly modular 5-membered ring formation using a combination of a three-component coupling reaction and a protodeboronative cyclization.

Copper(I) and palladium(II) complexes containing 5-acetyl-6-methyl-1,2,3,4-tetrahydropyrimidine-2-thione (L1), ethyl 4,6-dimethyl-2-thioxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate (L2), cis-5-acetyl-6-ethyl-5,6-dihydro-2-thiouracil (L3), and 5,6-dihydro-2-thiouracil (L4) have been synthesized. All complexes were characterized by elemental analysis, IR, 1H, and 13C NMR spectroscopy. To assign bands in the IR spectra of L1 and L2 and complexes with Cu(I) and Pd(II), deuterium substitution of movable protons at N-atoms was used. The crystal structures of two compounds, [Cu(L2)2Cl] and [Pd(L4)2Cl2], were determined by X-ray single-crystal and powder diffraction, respectively. In [Cu(L2)2Cl], copper has a rare coordination number of three and triangular surrounding of two neutral L2 molecules, coordinated through sulfurs, and chloride. In [Pd(L4)2Cl2], palladium has a standard square-planar geometry, formed by two uracil molecules and two chlorides. A new method for the synthesis of 5,6-dihydro-2-thiouracil, starting from β-aminopropionic acid, was suggested.

Regioselective bromination of methyl pyropheophorbide a at the C3 2 -position of the terminal double bond has been carried out as a one-pot two-step addition/elimination process. The elimination occurs with 100% stereoselectivity and bromovinyl 4 has E-configuration of the C3-double bond. The reactivity of unsaturated bromide 4 has been evaluated in the series of the Pd -catalyzed coupling reactions.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

aFrumkin Institute of Physical Chemistry and Electrochemistry of Russian Academy of Sciences, 199071 Moscow, Russia bLomonosov Moscow University of Fine Chemical Technology, 119571 Moscow, Russia cOrekhovich Institute of Biomedical Chemistry of Russian Academy of Medical Sciences, 119832 Moscow, Russia dIvanovo State University of Chemistry and Technology, 153000 Ivanovo, Russia @Corresponding author E-mail: joz@mail.ru

Complexes of formamide and dimethylacetamide with cadmium iodide, [Cd(HCONH2)2I2], [Cd(HCONH2)4I2], [Cd3(HCONH2)2I6], and [Cd(MeCONMe2)6][Cd2I6] and of 5-acetyl-6-methyl-1,2,3,4-tetrahydropyrimidine-2-thione (MP) with zinc iodide, [Zn(MP)(H2O)I2], were synthesized; their crystal structures were studied by X-ray diffraction. Unique transformations of cadmium iodide complexes with formamide were observed. Structural diversity of zinc and cadmium iodide complexes with (thio)amides is discussed in terms of donating ability of the ligands, steric requirements and sizes and polarizing power of the cations.

Platinum(II) and palladium(II) complexes of coproporphyrin-I tetraisopropyl ester and coproporphyrin-II tetraethyl ester, as well as platinum(II) complexes of mesopyropheophorbide a methyl ester and mesochlorin e(6) trimethyl ester were synthesized. Five of them (platinum(II) mesochlorin e(6) trimethyl ester is amorphous) were prepared as single crystals and structurally characterized by X-ray diffraction. The porphyrinates were used for sensitization of titania. The photocatalytic activity of the samples was studied in the reactions of methyl orange decomposition under UV irradiation (lambda = 250-400 nm) or visible light (lambda > 450 nm). The highest photocatalytic activity under UV radiation was found with the use of palladium(II) coproporphyrin-II tetraethyl ester. Under visible light, the best results were achieved for the titania-silica powder modified with platinum(II) coproporphyrin-II tetraethyl ester in the reaction of methyl orange decomposition carried out in the presence of sodium fluoride.

The asymmetric unit of the title compound, [Cd(C30H31N3O6)2](PF6)2·3H2O, contains one half-cation with the CdII center situated on a twofold rotational axis, one hexafluoridophosphate anion and two uncoordinated water molecules, one of which is also situated on a twofold rotational axis. The cations are associated into columns along the a axis through π–π interactions between the pyridine and benzene rings, with a centroid–centroid distance of 3.72 (5) Å. Intermolecular O—H⋯O, C—H⋯O and C—H⋯F hydrogen bonds consolidate the crystal packing.