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Relevance. The development of fermented herbal beverages will make it possible not only to process grain crops as efficiently as possible, but also to meet the needs of people with intolerance to milk components, as well as those who adhere to a vegetarian diet. As one of the directions, it is possible to offer production of fermented vegetable drinks with predetermined properties by enriching them with antioxidants of polyphenolic nature. These technologies will minimise the risks of non-communicable diseases in the Russian Federation and stabilise public health in the long term.Methods. Six samples of fermented herbal beverages were identified as objects of study, two of which were obtained by fermentation of wheat and barley grains using "Bifivit" starter, powdered flavonoid taxifolin was added to other two samples at the fermentation stage, while the last two used the hydroxypropyl-betacyclodextrin encapsulated form of taxifolin. Total flavonoid content using spectrophotometric method, antioxidant activity(AOA) using DPPH-method as well as bioavailability index and digestibility criterion were determined in all tested samples.Results. All the samples of fermented herbal beverages with taxifolin are characterized by sufficiently high flavonoid content. The samples containing encapsulated forms of the flavonoid have, on average, 7 to 8% lower values than the samples of herbal drinks containing the native form of the flavonoid. At the same time, the bioavailability index for the samples containing encapsulated forms of flavonoid was on average 40 to 42% higher, indicating the effectiveness of the encapsulation process. The highest values of antioxidant activity were characteristic of the plant drinks enriched with the initial form of taxifolin, which is probably due to the creation of a protective shell and a decrease in the AOA values by 10–12% on average in samples with encapsulated form. The process of fermentation of vegetable raw materials leads to an increase in their digestibility, as evidenced by the growth of the infusoria Tetrahymena pyriformis. Introduction of taxifolin into the formulation of drinks both in its original and encapsulated form increases the growth of protozoa by 187±4–315±3%.

Relevance.Bread products are socially important foodstuffs, physically and economically accessible for the majority of population groups in the Russian Federation and many other countries. One of the directions could be the enrichment of bakery products with natural antioxidants of plant origin. Polyphenolic substances, including flavonoids, have priority among plant antioxidants. Today several approaches to enrichment of bakery products with polyphenols and flavonoids are known, each of them characterised by their own advantages and disadvantages. The basis of this study was to evaluate the possibility of using different bakery enrichment approaches to obtain products with given antioxidant properties.Methods. Six samples of bakery products, five of which were enriched with food ingredients— sources of antioxidants— were identified as objects of research. The total content of polyphenols and flavonoids was determined in all the examined samples using spectrophotometric method as well as the antioxidant activity using DPPH-method.Results. Studies have shown that the use of crushed green tea leaves, cedar flour, whole-milled flour from germinated wheat grain as enriching agents allows a significant increase in the total content of polyphenols in the finished samples of baked products, by 46–75% in relation to the control. All the samples of enriched products could be classified as functional foods, as the satisfaction of the daily requirement for flavonoids was more than 15% of the recommended level. At the same time, the use of individual enriching substances such as taxifolin allows to significantly increase the antioxidant activity of baked products (more than by4 times) and with a high probability to steadily regulate it. In general, in all investigated samples of enriched bakery products increase ofthe antioxidant activity by more than 2 times in relation to the controlwas registered. The results confirmed the possibility and feasibility of using the proposed approaches of bakery products enrichment to obtain products with antioxidant properties.

There has been a significant increase in the oat (Avena sativa. L) consumption recently due to the new scientific data on dietary properties of oats, high content of polyphenols, especially Avenanthramides, and some flavonoids with an antioxidant effect. However, the thick layer of the cell wall in the hypoaleurone area and the uneven distribution of nutrients over the kernel determine the need to find effective technological solutions for their use in food production. The use of whole grain and its sprouting could be one of the possible solutions. Sprouting breaks difficult to digest grain complexes, thus making nutrients available for plant development and easier for human body intake. In the framework of this study, we propose to activate the process of grain sprouting by ultrasonic treatment of water used for preliminary grain soaking. The research results revealed that the proposed method accelerates accumulating of polyphenolic substances, phenolic acids and total antioxidant capacity. The mass fraction of polyphenolic substances in Avena sativa L. samples preliminarily aged in water treated with ultrasound (315W) for 2 minutes was 2.811 mg CAE/g, which is 4.64 times more than the mass fraction of the reference non-sprouted sample. Accumulation of phenolic acids at different treatment modes was intensified by 30.5% and more compared to the non-sprouted grain. Mathematical processing of the total antioxidant capacity (DPPH) results established a reasonable mode of ultrasonic water treatment used for grain soaking - 400 W for 2 minutes, the total antioxidant capacity will be 2.254 mg TEAC / g. Thus, the ultrasonic effect can be recommended as an intensifier in grain sprouting.

Possible risks associated with the accumulation and migration of mycotoxins during germination of crops are presented. The presence of an acceptable level of surface microflora of grain can, during germination, intensify the accumulation of mycotoxins, which later migrate into the finished product, making it dangerous for the consumer. It is noted that the process of germination of grain crops cannot be carried out without the stage of disinfection. Promising methods of grain disinfection using non-thermal effects of exposure and the results of our own research are given. It is noted that the concept of food safety in world practice today is aimed at preserving the main food ingredients and their properties. Thermal effects lead to an effective reduction in the development of microorganisms, but at the same time cause significant losses of thermolabile compounds and adversely affect the organoleptic, physicochemical and functional properties of the final product. Ultrasonic exposure, nanosecond electromagnetic pulses and exposure to cold plasma are proposed as disinfecting methods. The methods presented today are widely used in world practice. They allow not only to deactivate molds, but also to destroy the already formed aflatoxins in food products (use of cold plasma). Based on the foregoing, it can be said that the danger of pathogenic microflora ingress and aflatoxin accumulation in food products (especially whole grains) is still present, since even a minimal amount of them can cause global harm to public health, therefore, the search and development of new disinfection methods is an urgent problem modern production.

The article considers the possibility of using ingredients of plant origin in the production of enriched bakery products in order to increase the content of flavonoids in them, substances capable of improving the regulation of cellular metabolism and participate in protecting the human body from oxidative stress. As part of solving the issues of increasing the amount of flavonoids in the composition of the food matrix, bread and bakery products are the most optimal, because have a complex food matrix and contain all macronutrients in different ratios. With regular consumption of bakery products, they can become a real tool for replenishing micronutrients missing in the human diet or be a source of biologically active substances of directional action. As part of the research, two areas were studied: the use of enrichment technology with food ingredients rich in flavonoids (hygroquercithin and its micronized form) and an increase in the content of flavonoids at the expense of its own grain resources (whole-wheat flour from germinated wheat grain). The highest amount of flavonoids was observed in bread samples, both with the addition of DHA and micronized DHA, the number of flavonoids increased relative to the control 0.167 ± 0.002 mg EQ / g and 0.195 ± 0.004 mg EQ / g, respectively. Moreover, their content practically does not differ in quantity both in the crust and the subcortical layer, and in the crumb of bread samples. The use of whole-grain flour from sprouted wheat grain also leads to an increase in the amount of flavonoids both in the rind and subcortical layer, and in the crumb of bread samples. This value increases according to the percentage of whole-grain flour applied and is due to the content of flavonoids in it (0.14 ± 0.002 mg EQ / g).

The article considers the possibility of using whole-grain flour from germinated wheat grain as a raw material component containing easily digestible sugars, essential amino acids, vitamins and minerals. For the intensification of the germination process, the treatment of wheat at the acoustic source of elastic oscillations is used at a frequency of (22 ± 1.65) kHz and power of 340 W and an exposure time of 5 minutes. The obtained whole-ground flour from germinated wheat grain has a weighted average particle size of flour 177 ± 25 microns. This flour was used in the production of model bread samples by partial replacement of high-grade flour in the amount of 10–50%. Based on the determination of technological parameters, it was found that the use of whole-grain flour from germinated wheat grain increases the sugar-forming and gas-forming ability of the flour mixture, intensifies the fermentation process. It has little effect on the quantity and quality of gluten. The optimal value of the drop number was found for the first-grade baking wheat flour and whole-grain flour from germinated wheat in a ratio of 80:20, respectively. This ratio was also defined as the best organoleptic evaluation of laboratory test baking bread samples. The model sample had an attractive appearance, a convex brown, uniform porosity, non-sticky, elastic crumb, pronounced taste and aroma. The authors note that the improvement of the production technology of bakery products obtained using whole-grain flour from germinated wheat grain is possible by choosing the optimal dosage of introducing this type of raw material and monitoring the technological parameters of the process.

The article is devoted to the study of antioxidant activity (AOA) food ingredients (FI) containing fucoidan used as dressers bakery and dairy products, and evaluate their impact on the quality and persistence of the products. The use of FI possessing AOA in food production will ensure their functionality from the point of view of increasing the resistance of the body to noninfectious diseases. Objects of research were fucoidan from different manufacturers, as well as experimental samples of bread wheat and yoghurt-based products restored dry milk. Evaluation of antioxidant activity of FI based on fucoidan showed that the total concentration of antioxidants varies in significant range from (43,32 ± 0,2) to (69,17 ± 0,2) mg of ascorbic acid per 100 g was Also determined the effect of any FI on the organoleptic and physico-chemical quality parameters of bread and yogurt product in storage. The use of FI in the technology of bread contributes to the prolongation of periods of storage. Thus the deviation values increased humidity decreases by 1.3%, porosity – by 1.4%. In addition, we studied the temperature stability of fucoidan after baking bread. The residual content of his made up 0,196 ± 0.0015 mg/g when introducing 0.2 g. study of the effect of FI with fucoidan on the inhibition of the processes of molding bread confirmed the strong bactericidal properties of fucoidans, due to the high AOA. During storage of yoghurt for 120 hours was observed decrease in the activity of capacity operated of acidity that may be due to the action of FI.

The relevance of the topic lies in the task of providing the beverage industry with high quality feedstock. In the brewing industry there is the problem of water quality. To solve this problem is possible by implementation of modern achievements of science and technology ( ultrasonic water treatment in the stage production of malt in the process of soaking and germination of malting barley.In this regard, we have justified the use of targeted ultrasonic treatment of water at the stage of malt production in the process of soaking and germinating barley intended for obtaining a beverage such as beer. As a result of our studies, we have established a positive effect of ultrasound on water quality when certain conditions are created. Such conditions are the parameters of ultrasound exposure: power and processing exposure. We have revealed regularities associated with the mechanism of ultrasound action on water quality; The optimal valuesof the parameters of ultrasonic action are determined, which allow obtaining a given level of quality of water due to the achievement of certain values of such parameters as rigidity, pH and total microbial number. The positive influence of ultrasonic treatment on the quality and properties of water under certain conditions; the regularities and the effective parameters of this impact. We used ultrasonic device (UZTA O OM 4/22). Water treatment at a frequency of 22 kHz, a power of 180-240 W, 3-5 minutes exposure achieves positive effects on quality metrics such as: rigidity, which is reduced by 14-22% of the initial value; pH, which decreases to 0.28-0.35 units; total bacterial number, which is reduced by 6-7 times.

Objective. To estimate target organs state and endothelial function in patients with isolated ambulatory hypertension at work. Design and methods. 76 patients with hypertension at working place (AHwp) formed the 1st group, 42 patients with fi rstly diagnosed essential hypertension formed the 2nd group. Offi ce blood pressure (BP) was measured in all subjects. Also BP monitoring at work and at rest, echocardiography, duplex scanning of brachiocephal arteries, test of brachial artery temporary occlusion and endothelial function assessment were performed. Results. Patients of the 1st and 2nd groups had comparable risk factors. Patients with AHwp 24,1 % (p = 0,01) oftener showed diastolic dysfunction of left ventricle (LV). Intima-media thickness did not differ between groups but atheroma was found more frequently (for 13,2 %, p = 0,01) in subjects from the 1st group. Subjects with AHwp in comparison with those with essential hypertension rarely had normal endothelial function (for 26,1 %, p = 0,005), vasoconstrictive endothelial reaction on temporary occlusion was found oftener (for 30,3 %, p = 0,001) in 1st group subjects. Conclusions. Patients with masking hypertension had comparable rate of main risk factors, LV hypertrophy and brachiocephal atherosclerosis, but they showed more expressed diastolic dysfunction of LV and endothelial dysfunction as compared to patients with essential hypertension.

The reaction of lacunary arsenitotungstate [AsW9O33]9− with [M3S4(H2O)9]4+ in aqueous solution leads to the formation of the complex [{Mo3S4(H2O)5}(H2AsW9O33)2]10−. X-ray crystal structure analysis of its cesium salt of the composition Cs5.6K4.4[{Mo3S4(H2O)5}(H2AsW9O33)2]·19.15H2O (1) is reported. Similarly, the reaction of [AsW9O33]9− with [W3S4(H2O)9]4+ and NaAsO2 yields [{W3S4(H2O)5}(H2AsW9O33)(HAsW9O33AsOH)]9−. For K6.35(NH4)2.65[{W3S4(H2O)5}(H2AsW9O33)×(HAsW9O33AsOH)]·23.7H2O (2) the crystal structure is determined. In both compounds, the {M3S4}4+ cluster cores coordinate one polyoxometalate ion, which functions as a bridging ligand between two metal atoms, and one bidentate polyoxometalate. The other five coordination sites at the cluster core are occupied by water molecules. The complex anions form dimeric associates held together by hydrogen bonds and S...S contacts.

Crystallization of cobalt(II) chloride and S-(−)-1,1′-binaphtyl-2,2′-diamine (L) from an acetone solution has afforded a chiral complex [CoL*Cl2]·Me2CO (L* = the acetone diimine derivative of binaphtyldiamine). The compound has been structurally characterized.

The reaction between metallic iron and the incomplete cuboidal cluster [Mo3Se4(H2O)9]4+ in 2 M HCl gives the heterobimetallic cuboidal cluster with the new Mo3FeSe4 4+ core (exists in 2 M HCl as [Mo3(FeCl)Se4(H2O)9]3+ (UV/Vis λ (ϵ/M−1 cm−1): 500 sh(1085), 633(1216), 531(738), 880(223)); in 2 M Hpts as [Mo3(FeH2O)Se4(H2O)9]4+ (λ(ϵ/M−1cm−1)): 642(669), 528(1122)). No reaction was observed with [W3Q4(H2O)9]4+ (Q=S, Se). For the sulphur analogue, the structure of the 1∶1 adduct with the cucurbit[6]uril (CuC), {[Mo3(FeCl)S4(H2O)8Cl]pyH⊂CuC[6]}Cl3 · 11.25H2O was determined (Mo‐Fe 2.7067(19)A; Mo‐Mo 2.7723(14))A; Fe‐Cl 2.223(4)A).

Dark-brown plate crystals of the [Mn7(H2O)26{Nb4OTe4(CN)12} 2](OH)2·11H2O compound (1) were prepared by the reaction of an aqueous ammonia solution of the K6[Nb4OTe4(CN)12]{K2CO3{KOH{8H2O complex with a glycerol solution of manganese(II) nitrate. The structure of complex 1 was established by X-ray diffraction. Compound 1 has a polymer structure containing four types of manganese atoms. The nitrogen atoms of eight cyano groups of the tetranuclear niobium cluster are coordinated to the manganese atoms to form a {2,3,8}-connected three-dimensional network.

The reaction of PdCl(2) with [W3S4(H2O)9]4+ in the presence of hypophosphorous acid in 2 M HCl gives cuboidal cluster [W3(PdCl)S4(H2O)9]3+ (1) which undergoes condensation and crystallises from Hpts solutions as edge-linked double cubane cluster [{W3PdS4(H2O)9}2](pts)(8).19H2O (pts = p-toluenesulfonate) (1'). The substitution of Cl- in (1) by different ligands was explored. The Pd atom in the cluster shows an exceptionally high reactivity in the isomerisation of the hydrophosphoryl H2P(O)(OH), HP(O)(OH)2, HPPh(O)(OH) and HPPh2(O) molecules into the corresponding hydroxo tautomers HP(OH)2, P(OH)3, PhP(OH)2 and Ph2P(OH) stabilised by coordination at Pd. The reactions were followed by UV-Vis spectrophotometry and 31P NMR. Formation constants of the 1 : 1 coordination of [M3(PdCl)S4(H2O)9]3+ (M = Mo, W) with HP(OH)2 and As(OH)3 were obtained. The structures of cucurbit[6]uril (C36H36N24O12, CUC[6]) adducts [W3(PdP(OH)3)S4(H2O)8Cl]-(C36H36N24O12)Cl3.12.5H2O (2), and [W3Pd(PhP(OH)2)S4(H2O)7Cl2]2(C36H36N24O12)Cl4.9H2O (3) were determined by single-crystal X-ray diffraction.

The authors revealed features of metabolic syndrome diagnosis by means of various intradisciplinary criteria in locomotive crew workers. The locomotive crew workers, if compared to mounters, demonstrate 1.4 times more frequent excessive body weight, 1.6 times more frequent obesity, 1.4 times more frequent dyslipidemia, 2 times more common arterial hypertension. According to RSCS, metabolic syndrome in locomotive operators appeared more frequent--1.6 times than in IDF, 1.5 times than in ATP, ESN. Frequency of metabolic syndrome in males of stress occupations varies from 30% according to ATP, IDF, ESN to 49% according to RSCS--that is 2.5 times more frequent than in individuals with low occupational stress. Bioimpedometry revealed fluidsretention in 13% of train operators, water deficit in 24%, muscular mass deficiency in 55%. RSCS criteria are priority in interdisciplinary approach to metabolic syndrome evaluation in males under occupational stress. Assessment of visceral fat in locomotive crew workers helps to formulate purposeful prophylactic recommendations.

[Ni(dien)2]3[W4S4(CN)12]·20H2O and [Cu(dien)(Hdien)]2[W4S4(CN)12]·8H2O were obtained by evaporating water-ammonia solutions containing K6[W4S4(CN)12]·2H2O·2CH3OH, diethylene triamine, and NiCl2·6H2O or CuCl2·6H2O. The crystals of the complex compounds were obtained within 3 days. The complex compounds were characterized by IR spectroscopy and by XRD and elemental analysis. XRD data for the complex [Ni(dien)2]3[W4S4(CN)12]·20H2O are: triclinic system, $$P\overline 1 $$ , a = 14.671(2) A, b = 16.448(3) A, c = 19.814(3) A, α = 67.841(3)°, β = 68.996(3)°, γ = 67.527(3)°, V = 3961.6(11) A3, Z = 2; for the complex [Cu(dien)(Hdien)]2[W4S4(CN)12]·8H2O: monoclinic system, C2/c, a = 37.4290(1) A, b = 17.7370(1) A, c = 25.7370(2) A, β = 105.3840(2)°, V = 16474.02(16) A3, Z = 12.

The reactions of anionic molybdenum and tungsten cyanide cuboidal clusters with CuII and MnII salts afforded two new cyanide-bridged heterometallic coordination polymers with the composition [{Cu2(dien)2(CN)}2{Mo4Te4(CN)12}]⋅14.5H2O (1) and (H3O)3K[{Mn(H2O)2}2{Mn(H2O)2(NO3)}4{W4Te4(CN)12}2]·8H2O (2). The structures of these compounds were established by X-ray diffraction analysis. Compound 1 has a layered structure, in which the cuboidal cluster fragments {Mo4Te4(CN)12}6− are linked to the copper atoms of the dinuclear fragments {(H2O)(dien)Cu(μ-CN)Cu(dien)(H2O)} through the bridging CN groups. Coordination polymer 2 has a framework structure, in which the cluster fragments {W4Te4(CN)12}6− are linked to the manganese(II) aqua complexes of two types, viz., the dinuclear fragment {Mn(μ2-H2O)2Mn} and the tetranuclear cyclic fragment {(H2O)2Mn(μ2-NO3)}4, through the bridging CN groups.

The compound [Co(NH3)6]2[W4Se4(CN)12]·8.5H2O was obtained by evaporating an aqueous ammonia solution of K6[W4Se4(CN)12]·6H2O and CoCl2·6H2O complexes. The starting Co(II) of CoCl2·6H2O transforms into [Co(NH3)6]3+ when exposed to air in a water-ammonia medium. Crystal data: triclinic crystal system, a = 10.7750(8) A, b = 12.2843(9) A, c = 19.6539(14) A; α = 90.213(2)°, β = 99.910(2)°, γ = 114.737(1)°, V = 2319.1(3) A3, space group $$P\bar 1$$ , Z = 2, D x = 2.633 g/cm3.

Two new tetrahedral tungsten cyanide cluster compounds, [Cu(dien)]3[W4Te4(CN)12] · 9H2O (1) (dien=diethylenetriamine) and [Ni(en)(NH3)]3[W4Se4(CN)12] · 7.5H2O (2) (en=ethylenediamine), were synthesized by treating aqueous solutions of the saltlike cluster compound K6[W4Te4(CN)12] · 5H2O/K6[W4Se4(CN)12] · 6H2O with copper(II)/nickel(II) chloride in aqueous ammonia containing dien/en. The cyano-bridged layered coordination polymeric compounds were characterized by single-crystal X-ray diffraction analysis: monoclinic, space group P21 for 1; trigonal, space group R 3 for 2. Structures of 1 and 2 consist of infinite neutral layers of cluster components {W4Te4(CN)12}/{W4Se4(CN)12} connected, one another by {Cu(dien)} or {Ni(en)(NH3)} fragments, respectively.

Evaporation of aqueous ammonia solutions of K7[Mo4Te4(CN)12]·12H2O or K6[W4Te4(CN)12]·5H2O, copper(ii) chloride, and ethylenediamine afforded the isostructural heterometallic complexes [{Cu(en)2}2{Cu(en)2(NH3)}{M4Te4(CN)12}]·5H2O (M = Mo or W), which were characterized by IR and ESR spectroscopy and X-ray diffraction analysis.

Eight isostructural polymeric coordination compounds of the general formula [Ln(DMF)(H2O)4][Ln(DMF)2(H2O)4][M4Te4(CN)12]·DMF·nH2O (Ln = Er, Ho, Gd, or Sm; M = W or Mo) were prepared for the first time by evaporation in air of aqueous solutions containing the cuboidal telluride anionic complex of tungsten [W4Te4(CN)12]6– or molybdenum [Mo4Te4(CN)12]7–, lanthanide chlorides, and dimethylformamide. The resulting polymeric coordination complexes with layered structures were characterized by X-ray diffraction analysis and IR spectra. The magnetic susceptibilities of the gadolinium complexes were measured.

Dark-brown single crystals of the title compound 1 were obtained in high yield by layering a CuCl2 solution in 25% aqueous ammonia on a glycerol solution of K6[W4Te4(CN)12]·5H2O. The complex 1 was characterized by single crystal X-ray diffraction analysis and IR spectroscopy. The X-ray structure of 1 reveals a polymeric chain cyano-bridged cluster-metal coordination compound. The [W4Te4(CN)12]6− cluster anions are linked one to another by Cu2+ cations through coordination by nitrogen atoms of the CN groups.

Single crystals of [Zn(NH3)4]3[Mo4Te4(CN)12] (I) and [Cd(NH3)4]3[W4Te4(CN)12] (II) were obtained by applying solutions of K7[Mo4Te4(CN)12] · 11H2O and K6[W4Te4(CN)12] · 5H2O in aqueous ammonia over solutions of ZnCl2 and Cd(NO3)2 in glycerol and were characterized by X-ray diffraction analysis. The IR spectra and thermal properties of compounds I and II were examined.

The new cubane cluster complex K6[Ta4(μ4-O)(μ3-Te)4(CN)12]·KOH·4H2O was prepared from a mixture of TaTe4 and KCN by the high-temperature synthesis followed by crystallization from aqueous solutions. The compound was characterized by cyclic voltammetry, X-ray diffraction analysis, and IR, Raman, and electronic spectroscopy. A comparative study of the clusters [M4(μ4-O)(μ3-Te)(CN)12]6– (M = Nb or Ta) containing the μ4-O ligands was carried out. These clusters are the first molecular chalcogenide cubane complexes of Group V metals.

The compound [Mn(H2O)4]3[W4S4(CN)12]·nH2O (1) was prepared by the reaction of an aqueous solution of MnSO4 with a glycerol solution of KCs5[W4S4(CN)12]·4H2O. Complex 1 was characterized by X-ray diffraction analysis and IR spectroscopy. According to the X-ray diffraction data, the three-dimensional polymeric framework of 1 comprises only 24.2% of the unit-cell volume. The volume of the cavities per formula unit is 1664 A3. The cavities are occupied by highly disordered water molecules.

Crystal structures of two new compounds containing trigonal tellurium-bridged cluster fragments [Mo3(μ3-Te)(μ2-Te2)3]4+ were investigated. Crystal data for K4.5{[Mo3(μ3-Te)(μ2-Te2)3(CN)6]I}I1.5·3H2O: space group \(P\bar 3c1\), Z = 4, a = 13.280(1), c = 23.800(3) A, V = 3635.0(6) A3, d calc = 3.432 g/cm3, R 1 = 0.0335, wR2 = 0.0912 for 1378 I hkl > 2 σI from 3545 measured I hkl ; for Cs3{[Mo3(μ3-Te)(μ2-Te2)3(CN)6]I}·2H2O: space group P2 1 /n, Z = 2, a= 9.650(2) , b = 22.297(5), c = 27.446(7) A, β = 94.10(2)°, V = 5890(2) A3, d calc = 4.273 g/cm3, R 1 = 0.0384, wR 2 = 0.0744 for 957 I hkl > 2 σI from 3758 measured I hkl (Enraf-Nonius CAD-4 diffractometer, λMoKα, graphite monochromator). In both compounds, ionic pairs {[Mo3Te7(CN)6]I}3– with Teax...I– distances of 3.358-3.676 A are formed. In the potassium salt, the {[Mo3Te7(CN)6]I}3– anion pairs are linked by the additional Teeq⋯I– short contacts of 3.460 A into two-dimensional corrugated layers perpendicular to the c axis of the unit cell. The structure of the cesium salt is ionic with interstitial H2O molecules and double-layer closest packing of anions.

The crystal structure of (N2H5)2[Mo3S7I6]· 1.5H2O is investigated;triclinic crystals, a-10.029(2), b = 10.258(3), c =14.152(2) a, a =109.21(2), Β =106.14(1), γ =98.97(2)‡, V cell =1270.6(5) a 3, space group P1, Z =2, d calc =3.572 g/cm 3, CAD-4 diffractometer, λMoKα, 2θmax =50‡, N tot =4118, R(F) = 0.0554, wR(F2) = 0.1365 for 3057 Fhkl 4Σ(F). The cluster onions are united into centrosymmetric dimers with distances 3Sax...I 3.324(5)-3.473(4) a. The dimers, in turn, form a three-dimensional framework with cations and solvate water molecules in the cavities due to additional contacts Seq...I and Sax...I 3.624(4)-3.785(4) a. The hydrogen bonds formed in the structure are N(N2H5)...O(H2O) and N(N2H5)...I 2.78(4)-2.96(8), 3.64(3)-3.75(3) a. The nonbonding interactions completely determine the crystal structure.

N,N-Dinitro derivatives of alkylurethanes, benzamide, andp-toluenesulfamide were synthesized for the first time. Their reactions with ammonia afforded the ammonium salt of dinitramide in 44–85% yields.

In the layered structure of the title compound, [Er2(C2O4)3(H2O)6]·4H2O, the Er atoms are bridged by oxalate ligands. Each Er atom coordinates to six O atoms from three oxalate ligands, and three water mol­ecules. The layers are parallel to the ac plane and four disordered water mol­ecules of crystallization are situated between the layers.

Four new chalcogenide molybdenum and tungsten cubane clusters (NH4)6[M4Q4(CN)12]·6H2O (M=Mo or W; Q=S or Se) were prepared by high-temperature reactions of the triangular M3O7Br4 complexes with KCN at 430 °C followed by crystallization from aqueous solutions of ammonium acetate. The molecular and crystal structures of (NH4)6[Mo4S4(CN)12]·6H2O, (NH4)6[W4S4(CN)12]·6H2O, and (NH4)6[W4Se4(CN)12]·6H2O were established by X-ray diffraction analysis. The mixed-valence cubane clusters are diamagnetic and isostructural and have the symmetryT d . The clusters were characterized by IR and electronic spectroscopy. The data of cyclic voltammetry demonstrated that the [M4Q4(CN)12] n− clusters exist in three oxidation states from the most oxidized (n=6; 10 cluster electrons) to the most reduced electron-precise 12-electron species (n=8).

Reactions of the incomplete cuboidal clusters [M3Q4(acac)3(py)3]+ (M = Mo, W; Q = S, Se) with group 14 and 15 metal complexes with the s2p0 electronic configuration (AsPh3, SbPh3, SbCl3, SbI3, PbI3-, SnCl3-) led to heterometal incorporation with the formation of cuboidal clusters of the type [M3(EX3)Q4(acac)3(py)3]n+ (n = 0 for Sn, Pb; n = 1 for As, Sb), whose structures were determined by X-ray diffraction. The cuboidal clusters can be described as complexes of the cluster tridentate ligand [M3Q4(acac)3(py)3]+ (mu2-chalcogen atoms as donors) with the EX3, where the E atom attains a distorted octahedral coordination. Analysis based on the bond distances E-Q gives the following sequence of affinity: As < Sb; Pb < Sn approximately Sb; SbPh3 < SbI3 approximately SbCl3; W3S4 < W3Se4. Interaction energies at the gas phase between [W3Q4(acac)3(py)3]+ (Q = S, Se) and SbX3 (X = I, Ph) were computed at the DFT level (BP86/TZP). The magnitude of the interaction depends strongly on the substituents at Sb, and the replacement of iodine by the phenyl group decreases the interaction energy from -9.21 to -2.70 kcal/mol and from -12.73 to -3.85 kcal/mol for the W3SbS4 and W3SbSe4 cores, respectively.

Heating WTe(2), Te, and Br(2) at 390 degrees C followed by extraction with KCN gives [W(3)Te(7)(CN)(6)](2-). Crystal structures of double salts Cs(3.5)K{[W(3)Te(7)(CN)(6)]Br}Br(1.5).4.5H(2)O (1), Cs(2)K(4){[W(3)Te(7)(CN)(6)](2)Cl}Cl.5H(2)O (2), and (Ph(4)P)(3){[W(3)Te(7)(CN)(6)]Br}.H(2)O (3) reveal short Te(2)...X (X = Cl, Br) contacts. Reaction of polymeric Mo(3)Se(7)Br(4) with KNCSe melt gives [Mo(3)Se(7)(CN)(6)](2-). Reactions of polymeric Mo(3)S(7)Br(4) and Mo(3)Te(7)I(4) with KNCSe melt (200-220 degrees C) all give as final product [Mo(3)Se(7)(CN)(6)](2)(-) via intermediate formation of [Mo(3)S(4)Se(3)(CN)(6)](2-)/[Mo(3)SSe(6)(CN)(6)](2-) and of [Mo(3)Te(4)Se(3)(CN)(6)](2-), respectively, as was shown by ESI-MS. (NH(4))(1.5)K(3){[Mo(3)Se(7)(CN)(6)]I}I(1.5).4.5H(2)O (4) was isolated and structurally characterized. Reactions of W(3)Q(7)Br(4) (Q = S, Se) with KNCSe lead to [W(3)Q(4)(CN)(9)](5-). Heating W(3)Te(7)Br(4) in KCNSe melt gives a complicated mixture of W(3)Q(7) and W(3)Q(4) derivatives, as was shown by ESI-MS, from which E(3)[W(3)(mu(3)-Te)(mu-TeSe)(3)(CN)(6)]Br.6H(2)O (5) and K(5)[W(3)(mu(3)-Te)(mu-Se)(3)(CN)(9)] (6) were isolated. X-ray analysis of 5 reveals the presence of a new TeSe(2-) ligand. The complexes were characterized by IR, Raman, electronic, and (77)Se and (125)Te NMR spectra and by ESI mass spectrometry.