Crystal structure and Hirshfeld surface analysis of the anionic tetrakis-complex of lanthanum(III) NMe4LaL 4 with the CAPh-ligand dimethyl (2,2,2-trichloroacetyl)phosphoramidate

The anionic tetrakis-complex of lanthanum(III) NMe4LaL 4 with the CAPh-ligand dimethyl (2,2,2-trichloroacetyl)phosphoramidate (HL), namely, tetramethylammonium tetrakis{2,2,2-trichloro-1-[(dimethoxyphosphoryl)imino]ethanolato}lanthanum(III), (C4H12N)[La(C4H6Cl3NO4P)4], has been synthesized, crystallized and structurally characterized by X-ray diffraction. The lanthanide ion is surrounded by four anionic, bis-chelating CAPh ligands forming the complex anion with a coordination number of eight for La3+ and NMe4 + as the counter-ion. The coordination polyhedron of the La3+ ion was interpreted as a triangular dodecahedron.

Amine-based synthesis of Fe3C nanomaterials: mechanism and impact of synthetic conditions

Iron-based catalysts are a preferred variant of metal catalysts due to the high abundance of iron on earth. Iron carbide has been investigated in recent times as an electrochemical catalyst due to its potential as a great ORR catalyst. Using a unique amine-metal complex anion composite (AMAC) method, iron carbide/nitride nanoparticles (Fe3C and Fe3−x N) were synthesized through varying several reaction parameters. While the synthesis is generally quite robust and can easily afford phase pure Fe3C, it now has been shown that the particle size, morphology, excess carbon, and amount of nitrogen in the resulting nanomaterials can readily be tuned. In addition, it was discovered that Fe2N can be synthesized as an intermediate by stopping the reaction at a lower heating temperature. These nanomaterials were tested for their electrochemical activity in oxygen evolution reactions (OER).

Broadening the scope of uranyl photoreactivity: The oxidation of a uranyl complex anion in solid-state materials

Reported are the syntheses, structural characterizations and luminescence properties of three novel [UO2Cl4]2 bearing compounds containing substituted 1,1’-dialkyl-4,4’-bipyridinum dications (i.e. viologens). These compounds undergo photoinduced luminescence quenching upon exposure to UV radiation. Kinetic analyses indicate the degree of quenching follows a second-order rate law with a rate constant dependent on viologen substituent. This phenomenon is proposed to involve the formal transfer of one electron from the [UO2Cl4]2- to the viologen species. This proposed mechanism is supported through a series of calculations and computational work including Rehm-Weller analysis, time-dependent density functional theory (TD-DFT), and density of states (DOS). This work constitutes the first study of an oxidized uranyl complex anion which expands the conventional understanding of uranyl photoreactivity.

Synthesis, Structure, and Radioprotective Activity of the Palladium (II) Complex With Mexidol

New complex compounds of palladium (II) with biologically active ligand 2 - ethyl - 6 methyl - 3 - hydroxy-pyridine - mexidol in acidic medium (pH = 5,3) of the following composition have been synthesized – (C8H12O⊕N)2 [PdCl4]. In this case, the ligand is protonated and as a single-charged cation occupies an external coordination sphere. The structure of the complex is proved by X-ray structure analysis. It is shown that the structure is constructed of an isolated complex anion [PdCl4]2- and cation C8H12O⊕N. The square planar coordination of the palladium atom is formed from three chlorine atoms and the formed tetraacidoanion ligand forms a hydrogen bond. The average length of Pd-Cl bond is 2, 3030 Α°, there are no deviations from 900 valence angles of Cl-Pd-Cl. The palladium atom is not shifted from the plane coordination polyhedron (square) and therefore trance angles of Cl-Pd-Cl are 1800. Two different lengths -2,289 Α° and 2,713 Α° of hydrogen bonds are related to the geometric location of the ligand functional group. The obtained 2 – ethyl – 6 – methyl – 3 -hydroxypyridinetrachloro - palladium - mexidazole was tested for radioprotective properties. Toxicity of the preparation is LD50 - 240 mg/kg of animal weight. Toxicological studies of mexidazole in mice, rats and dogs did not reveal cardiotoxic, immunotoxic, embryonic, nephrotoxic, hematoxic and other types of side effects. Mexidazole is removed from the body with urine 5-8 hours after intravenous injection. The carried out biological test showed that the compound, along with radioprotective properties, has some antitumor activity.

Synthesis, Structure, and Radioprotective Activity of the Palladium (II) Complex with Mexidol

New complex compounds of palladium (II) with biologically active ligand 2 - ethyl - 6 methyl - 3 - hydroxy-pyridine - mexidol in acidic medium (pH = 5,3) of the following composition have been synthesized – . In this case, the ligand is protonated and as a single-charged cation occupies an external coordination sphere. The structure of the complex is proved by X-ray structure analysis. It is shown that the structure is constructed of an isolated complex anion – and cation . The square planar coordination of the palladium atom is formed from three chlorine atoms and the formed tetraacidoanion ligand forms a hydrogen bond. The average length of Pd-Cl bond is 2, 3030 , there are no deviations from 900 valence angles of Cl-Pd-Cl. The palladium atom is not shifted from the plane coordination polyhedron (square) and therefore trance angles of Cl-Pd-Cl are 1800. Two different lengths -2,289 and 2,713 of hydrogen bonds are related to the geometric location of the ligand functional group. The obtained 2 – ethyl – 6 – methyl – 3 -hydroxypyridinetrachloro - palladium - mexidazole was tested for radioprotective properties. Toxicity of the preparation is LD50 - 240 mg/kg of animal weight. Toxicological studies of mexidazole in mice, rats and dogs did not reveal cardiotoxic, immunotoxic, embryonic, nephrotoxic, hematoxic and other types of side effects. Mexidazole is removed from the body with urine 5-8 hours after intravenous injection. The carried out biological test showed that the compound, along with radioprotective properties, has some antitumor activity.

Investigation of Substitution Reactions Between Zinc(II) Complexes with Different Geometries and N-bonding Nucleophiles

Aims: Investigation of interactions between zinc(II) complexes with different geometrical structures and relevant nitrogen donor nucleophiles at physiological pH. Background: The lack of clear distinction between the therapeutic and toxic doses of platinum drugs is a major challenge for the design of novel non-platinum DNA and protein targeting metal-based anticancer agents. The non-platinum antitumor complexes could be alternatives to platinum-based drugs due to their better characteristics and different mechanism of action. Objective This study could provide more information for the design of future zinc-based anticancer drugs, as well as providing a better understanding of the mechanism of interactions between Zn(II) complexes and nitrogen-donor nucleophiles (important from a medical point of view) and clarifies the changes in geometrical structures of zinc(II) that are referred to structure-reactivity correlation Methods Mole-ratio method and UV-Vis spectroscopic kinetic method were applied in this study. Objective : This study could provide more information for the design of future zinc-based anticancer drugs, as well as providing a better understanding of the mechanism of interactions between Zn(II) complexes and nitrogen-donor nucleophiles (important from a medical point of view) and clarifies the changes in geometrical structures of zinc(II) that are referred to structure-reactivity correlation Methods Mole-ratio method and UV-Vis spectroscopic kinetic method were applied in this study. Result: The results indicated additional coordination of chlorides in the first coordination sphere with changes in coordination geometry and formation of the octahedral complex anion [ZnCl4(en)]2- while an excess of chloride didn’t affect the square-pyramidal structure of [ZnCl2(terpy)]. The substitutions of studied complexes and relevant nucleophiles proceed in two consecutive reaction steps that depend on the nucleophile concentration. Octahedral complex anion [ZnCl4(en)]2- forms rapidly, and all substitution processes of this complex species should be considered. We assume that the first reaction step is accompanied by the dissociation of chloride ligands. Nucleophile 1,2,4-triazole have shown the highest affinity toward [ZnCl2(en)], and rates of both steps are almost the same value, which indicates parallel reactions. Conclusion: The different order of reactivity of relevant N-donor ligands toward [ZnCl2(en)] and [ZnCl2(terpy)] complexes for the first reaction step occurred due to the influence of different geometrical structures of complexes. In contrast, low reaction rates for the second reactions of [ZnCl2(en)] complex with imidazole and pyrazine were a consequence of interconversion between octahedral and tetrahedral structure during substitution processes.

Crystal structure and Hirshfeld surface analysis of poly[[bis[μ4-N,N′-(1,3,5-oxadiazinane-3,5-diyl)bis(carbamoylmethanoato)]nickel(II)tetrapotassium] 4.8-hydrate]

The title compound, {[K4Ni2(C7H6N4O7)2]·4.8H2O} n , was obtained as a result of a template reaction between oxalohydrazidehydroxamic acid, formaldehyde and nickel(II) nitrate followed by partial hydrolysis of the formed intermediate. The two independent [Ni(C7H6N4O7)]2– complex anions exhibit pseudo-C S symmetry and consist of an almost planar metal-containing fragment and a 1,3,5-oxadiazinane ring with a chair conformation disposed nearly perpendicularly with respect to the former. The central NiII atom has a square-planar N2O2 coordination arrangement formed by two amide N and two carboxylate O atoms. In the crystal, the nickel(II) complex anions form layers parallel to the ab plane. Neighboring complex anion layers are connected by layers of potassium cations for which two of the four independent cations are disordered over two sites [ratios of 0.54 (3):0.46 (3) and 0.9643 (15):0.0357 (15)]. The framework is stabilized by an extensive system of hydrogen bonds where the water molecules act as donors and the carboxylic O atoms, the amide O atoms and the oxadiazinane N atoms act as acceptors.