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Rationale: Cluster forms of rhenium sulfides have important practical applications as catalysts in oil refining and thus present high interest. However, only a limited number of rhenium sulfide clusters have been described previously. It is known that cluster formation actively occurs under conditions of laser desorption–ionization; nevertheless, detailed studies of rhenium sulfides under such conditions were apparently not conducted previously. Methods: A sample of natural rhenium sulfide, collected from the fumarolic field of Kudriavy volcano (Iturup island, Russia) in 2002, was investigated using the laser desorption–ionization mass spectrometry method. The formed rhenium sulfide clusters were registered by a time‐of‐flight detector and identified programmatically using the software developed in IPCE RAS. The identification involved a comparison of the distribution of isotopic peak intensities, observed in the resulting mass spectra, with the theoretical probabilities of occurrence of various isotopologues for hypothetical rhenium sulfide species. Results: Over 60 rhenium sulfide clusters of RexSy+ and RexSyOz− types containing up to 10 rhenium atoms were formed when a sample of natural rhenium sulfide was exposed to laser desorption–ionization conditions. Several isolated heterometallic ReXMoSY+ and ReXMoSYOZ− clusters containing up to eight rhenium atoms were additionally observed in the resulting mass spectra. The species with compositions, for which the electrically neutral analogs are known, apparently were the most stable rhenium sulfide clusters among the detected ones. Conclusions: The obtained data allowed summarizing the patterns of formation of rhenium sulfide clusters under conditions of laser desorption‐ionization. The ability of rhenium and sulfur to form cluster species containing from 7 to 10 atoms of rhenium was likely discovered for the first time. The majority of the rhenium sulfide clusters described in this study, notably RexSy+ ions containing over seven atoms of rhenium, were apparently not observed previously. [ABSTRACT FROM AUTHOR]

Rationale: Phosphorotungstic acid (PTA) has many applications, especially in the field of catalysis, due to its structural properties. However, the structure of PTA is studied mainly using theoretical methods. Matrix‐assisted laser desorption/ionization (MALDI) has the potential to be an effective method for the experimental study of heteropolyacids. Limitations of MALDI are the high molecular weight of the particles and the complex distribution of isotopic peak intensities. Both problems can be solved by automatically identifying observed signals by generating hypothetical molecular formulas and estimating their isotopic distributions. Methods: Phosphotungstic acid was studied under conditions of laser desorption/ionization in the absence and in the presence of the matrix. Three types of matrices were used: 2,5‐dihydroxybenzoic acid in water, α‐cyano‐4‐hydroxycinnamic acid in acetonitrile, and sinapic acid (SA) in tetrahydrofuran. Part of the peaks in the resulting mass spectra was identified using in‐house developed software that implements the automated isotopic distribution brute force. Results: The most informative mass spectra were obtained using SA as the matrix, which enabled the detection of particles containing PTA dimers for the first time. The compositions of particles incorporating PTA dimers were determined in an automated manner and can be written as [H3PW12O40]2·2H2O (m/z = 5791.2 Da) and [H3PW12O40]2·4H2O (m/z = 5836.5 Da). Other observed species included (WO3)n·PO3−, HPO2·(WO3)n, and WO2·(WO3)n clusters, with the latter containing W in mixed oxidation states. Conclusions: The combined use of MALDI and an automated identification procedure provided valuable experimental data on the structure and fragmentation of phosphotungstic acid. To the best of our knowledge, this study was the first to report on particles containing phosphotungstic acid dimers. [ABSTRACT FROM AUTHOR]

CuI-Catalyzed amination of 2-bromo-, and 2-, 3-, and 4-iodopyridines with tri- and tetraamines aimed at the synthesis of N, N′-diheteroaryl derivatives was studied. A strong dependence of the product yields on the nature of starting compounds and the ligand used was observed. The increase in the number of ethene-1,2-diamine fragments in the polyamine structure led to the increase in the yields of polyheteroarylated compounds, whereas propane-1,3-diamine fragments favored the formation of monopyridinyl derivatives and promoted the heteroarylation of the secondary amino groups. 2-Iodopyridine, as a more reactive compound, readily formed N, N-diarylated products. The best yields of the target N, N′-dipyridin-2-yl derivatives were 76% in the case of the triamine and 68% in the case of the tetraamine. A comparison of CuI- and Pd0-mediated heteroarylation of polyamines was also presented. [ABSTRACT FROM AUTHOR]