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The change in the composition and content of phenolic compounds in the leaves and racemes of Hedysarum alpinim L. and H. flavescens Regel et Schmalh., introduced into the forest-steppe zone of Western Siberia were studied. On the example of H. alpinim, the changes in the content of phenolic compounds depending on the year of harvest and on the plant organ (leaves, racemes) were studied. The content of individual substances (gallic, chlorogenic acids, mangiferin, hyperoside, rutin, avicularin and 17 components of a phenolic nature) and the content of phenolic compounds by groups (hydroxycinnamic and hydroxybenzoic acids, xanthones and flavonols) were determined. Differences in the content of phenolic compounds by groups (in mg / 100 g) were found between the two species of the genus Hedysarum L.: xanthones and flavonols (up to 4614.9±63.7 and 1280.0±6.7, respectively) in leaves and xanthones (up to 847.9±29.8) in racemes in H. alpinim accumulated more than xanthones and flavonols (2911.6±79.0 and 976.2±0.5, respectively) in leaves and xanthones (76.2±2.5) in racemes H. flavescen. In the leaves of H. flavescens, in comparison with the leaves of H. alpinim, the content of hydroxybenzoic and hydroxycinnamic acids prevails. The leaves of the studied species accumulate the most hydroxycinnamic acids and xanthones, while the racemes accumulate the most flavonols. The content of hydroxybenzoic acids, xanthones, and flavonols H. alpinim varied significantly depending on the year of observation., Изучали изменение состава и содержания фенольных соединений в листьях и соцветиях Hedysarum alpinim L. и H. flavescens Regel et Schmalh., интродуцированных в лесостепную зону Западной Сибири. На примере H. alpinim исследовали изменение содержания фенольных соединений в зависимости от года сбора и от органа растения (листья, соцветия). Определяли содержание индивидуальных веществ (галловой, хлорогеновой кислот, мангиферина, гиперозида, рутина, авикулярина и 17 компонентов фенольной природы) и содержание фенольных соединений по группам (оксикоричные и оксибензойные кислоты, ксантоны и флавонолы). Между двумя видами рода Hedysarum L. были обнаружены различия по содержанию фенольных соединений по группам (в мг/100 г): ксантонов и флавонолов (до 4614.9±63.7 и 1280.0±6.7, соответственно) в листьях и ксантонов (до 847.9±29.8) в соцветиях у H. alpinim накапливалось больше, чем ксантонов и флавонолов (2911.6±79.0 и 976.2±0.5, соответственно) в листьях и ксантонов (76.2±2.5) в соцветиях H. flavescen. В листьях H. flavescens по сравнению с листьями H. alpinim превалирует содержание оксибензойных и оксикоричных кислот. В листьях изученных видов накапливается больше всего оксикоричных кислот и ксантонов, в соцветиях – флавонолов. Содержание оксибензойных кислот, ксантонов и флавонолов H. alpinim значительно варьировало в зависимости от года наблюдения.

In the article through the prism of the fate of E.A. Karmanov, a church publisher, editor and bibliophile, shows the complex process of survival of Russian church history science in the Soviet period. Deprived of the possibility of development, it turned out to be focused on the task of preserving its pre-revolutionary heritage and new manuscript evidence, which was to become material for future research. Under these conditions, the role of collectors and keepers of the book culture of the church became very important, as was E.A. Karmanov (1927 1998).

The paper considers the mathematical model of liquid motion in straight-line capillaries. The proposed mathematical model shows the liquid motion in slit-like capillaries, with regard to the density, viscosity and surface tension of liquids, the capillary size, and the angle of capillary inclination to the horizontal. The modeling results are proved by full-scale experiments.

The paper provides a brief review of modern sources of ultraviolet (UV) radiation used in fluorescent penetrant testing (FT). The differences in implementation of the method with different radiation sources (excilamps, mercury UV lamp and LED UV lamp) are revealed experimentally. It is shown that the XeCl excilamp is not inferior to other sources of UV radiation used in FT.

Cleanliness of the test surface is of particular importance in liquid penetrant testing. The surface cleanliness implies both the quality of surface cleaning from polluting substances, for example, oil, and the quality of its treatment, i.e. surface roughness. The surface roughness parameter increased to more than Rz = 20 μm can lead to unreliable test results since each groove on a rough surface will be a capillary for liquid spreading. Therefore, it will be difficult to completely remove the penetrant from the surface of the test object while removing its excess, which causes an indicator background of the surface and complicates defect detection. The study aims to determine the effect of liquid wettability on liquid penetrant testing results depending on the surface roughness. The paper proposes a mathematical model of liquid spreading on the rough surface depending on physicochemical properties of the liquid itself and material properties of the test object. The numerical modelling of the process is performed. The modelling results are confirmed experimentally, and statistical processing of the experimental results is performed.

Nondestructive penetrant testing is effective, and in some cases, it is the only possible method of accidents prevention at high-risk sites. But in nowadays liquid-filled discontinuity model has not been adequately studied. Hydrodynamics in the open-end capillaries characterize the flow of liquids using the methods of leak detection. To detect surface discontinuities that are capillary, capillary flaw detection methods are used. Until now, the theoretical relation l = l (t) has not been find out. This relation makes it possible to calculate the absorption kinetics in any capillary at all its stages, which would coincide with experimental data with high accuracy. The studies show that the time of filling the capillaries by liquid is usually higher than the theoretically predicted one. Therefore, revealing the regularities of filling capillaries with liquids to the maximum depth and the duration of filling the capillary with liquid by a given depth is an actual task. The authors suggest a model for determining the velocity of fluid in dead-end and open-end and through capillaries, which take into account the fractal topology of the surface.

New radical-cation salts based on bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF or ET) were synthesized: (ЕТ)2[8,8′-Br2-3,3′-Fe(1,2-C2B9H10)2] (1) and (ЕТ)[8,8′-I2-3,3′-Fe(1,2-C2B9H10)2] (2). Their crystal structures were studied by X-ray analysis, electroconducting and magnetic properties were measured in a wide temperature range. Salts (1) and (2) appeared to be the first radical-cation salts with [8,8′-I2-3,3′-Fe(1,2-C2B9H10)2]- and [8,8′-Br2-3,3′-Fe(1,2-C2B9H10)2]- anions, respectively. In the literature [8,8′-I2-3,3′-Fe(1,2-C2B9H10)2]- and [8,8′-Br2-3,3′-Fe(1,2-C2B9H10)2]- anions are presented for the first time. Salts (1) and (2) were found to be paramagnetic. Their room temperature conductivities were 2 and 1·10−6 Ohm−1cm−1, respectively.

The generation of Br-bridged complex of cobalt bis(1,2-dicarbollide) (8,8′-μ-Br-3,3′-Co(1,2-C2B9H10)2) and its reactions with arenes and some nucleophiles were studied. The complex 8,8′-μ-Br-3,3′-Co(1,2-C2B9H10)2 can be generated in situ via the action of 8-monobromo derivative of cobalt bis(1,2-dicarbollide) and AlX3 (X = Cl, Br) in different aromatic solvents. This unstable complex was characterized by 11B NMR spectroscopy for the first time. Its reactions with an appropriate arene led to [8-Br-8′-Ar-3,3′-Co(1,2-C2B9H10)2]- species even without addition of an activating Lewis base. Reactions of 8,8′-μ-Br-3,3′-Co(1,2-C2B9H10)2 with S- and N-nucleophiles (thioxane, morpholine) in benzene afforded the corresponding charge-compensated derivatives (8-Br-8′-Y-3,3′-Co(1,2-C2B9H10)2) as well as [8-Br-8′-Ar-3,3′-Co(1,2-C2B9H10)2]- species.

A new radical cation salt of bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) with iron(III) bis(1,2-dicarbollide) 8,8´-dichloro derivatives, that is (BEDT-TTF)2[8,8´-Cl2-3,3´-Fe-(1,2-C2B9H10)2], was synthesized. Its electroconducting and magnetic characteristics were studied, molecular and crystal structures were determined. The electroconductivity of crystals at room temperature was σ293 ~5 Ω–1 cm–1, which is close to the corresponding value for the salt of cobalt bis(1,2-dicarbollide) dichloro derivative and is considerably higher than the electroconductivity of a similar salt of unsubstituted iron bis(1,2-dicarbollide). The measurements of magnetic susceptibility at 2—300 K showed that this salt is paramagnetic.

The overview of penetrant testing quality control is considered. Disadvantages of methods of manufacturing metal check samples are identify, e.g. the implementation of several defects of different sensitivity classes on a single sample. The paper addresses the technology of application of universal nonmetallic reference test blocks containing several artificially-induced defects in the form of cracks of different sensitivity classes for liquid penetrant testing to evaluate the performance of liquid penetrant testing.

The variants of test panels that are made from a nonmetal for capillary nondestructive testing, where several flaws that correspond to different classes of sensitivity were represented, have been considered. The first variant considers the cracks with an exit to the side surfaces of the panel; in the second variant, cracks are formed in the central range of the panel surface. Splitting the test panel in two allows evaluation of nondestructive testing materials for flaw detection or the comparison of test kits. These variants of test panels may act as test sample, because the flaws are normalized parameters. Epoxy adhesive was chosen as the material of the test panel, where flaws are made by etching the metal with the required size.

Reactions of 8,8´-μ-iodo-3-commo-3-cobalta[bis(1,2-dicarba-closo-dodecaborane)] (8,8´-μI-3,3´-Co(1,2-C2B9H10)2) with aryl halides (fluoro-, chloro-, bromo-, iodo-, and o-dichlorobenzenes) were studied. The reaction of 8,8´-μ-I-3,3´-Co(1,2-C2B9H10)2 with these reagents proceeded only in the presence of sterically hindered Lewis bases with the cleavage of the bridging B—I bond and the formation of the corresponding anionic 8-aryl-8´-iodo derivatives of cobalt bis(1,2-dicarbollide). X-ray diffraction studies were carried out for the charge-compensated 8´-iodo-8-(4,1-oxathian-1-ium)icosahydro-1,1´,2,2´-tetracarba-3-commo-cobaltacloso-tricosaborate and the anionic tetramethylpiperidinium 8´-(3,4-dichlorophenyl)-8-iodoicosahydro-1,1´,2,2´-tetracarba-3-commo-cobalta-closo-tricosaborate. The X-ray diffraction data showed that the molecule of the former compound has the gauche conformation, whereas the anionic complex is in the trans conformation.

Two approaches for the preparation of 8-iodo-8′alkoxy substituted cobalt bis(1,2-dicarbollides) were studied. The reactions of the 8-iodo-8′-hydroxy ([1]−) and 8,8′-dihydroxy ([2]−) derivatives of cobalt bis(dicarbollide) anion with alkylhalogenides were investigated. A new one step protocol for the preparation of cobalt bis(1,2-dicarbollide) iodonium bridged compound [μ-8,8′-I-3,3′-Co(1,2-C2B9H10)2] (3) was worked up. The reactions of compound 3 with various primary alcohols (methanol, ethanol, propargyl alcohol, 3-butyn-1-ol, ethylene glycol and 2-bromoethanol) led to the title ethers with good yields. Compound Cs[8-I-8′-OH-3,3′-Co(1,2-C2B9H10)2] (Cs[1]) was determined by single-crystal X-ray diffraction and it was found to be a coordination 2D polymer in a solid state.

A series of novel conjugates of cobalt bis(1,2-dicarbollide)(-I) with 5-ethynyl-2′-deoxyuridine and its cyclic derivatives were synthesized. Conjugates with 5-ethynyl-2-deoxyuridine were prepared by the direct Sonogashira coupling of a series of cobalt bis(1,2-dicarbollide)(-I) terminal alkynes and 5-iodo-2′-deoxyuridine. Their furo[2,3-d]pyrimidin-2(3H)-one isomers were obtained either by intermolecular cyclization of the above conjugates or by Sonogashira coupling using Pd/C as a catalyst. Action of ammonia on these furo[2,3-d]pyrimidin-2(3H)-one conjugates resulted in pyrrolo[2,3-d]pyrimidin-2(3H)-one conjugates. Most of the designed compounds have shown low cytotoxicity in several cell lines. Some 5-ethynyl-2-deoxyuridine and furo[2,3-d]pyrimidin-2(3H)-one conjugates have also presented antiviral activity.

Ways of manufacturing nonmetallic control samples for capillary flaw detection are described. Several cracks, corresponding to different classes of sensitivity, are produced in one sample. A positive effect is achieved by creating a base of a nonmetal material – epoxy adhesive, in which the defects are obtained by etching foil of the required size. The results of tests of such control samples on a multiplicity of use and temperature effects are presented.

Radical cation salts of bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) and bis(methylenedithio)tetrathiafulvalene (BMDT-TTF) with the 8,8′-dichloro derivative of cobalt bis(1,2-dicarbollide) (BEDT-TTF)2[8,8′-Cl2-3,3′-Co(1,2-C2B9H10)2] (1) and (BMDT-TTF)4[8,8′-Cl2-3,3′-Co(1,2-C2B9H10)2] (2) were synthesized and their crystal structures and electrocon-ducting properties were determined. The synthesized radical cation salts are semiconductors with the conductivity σ293 = 1.5 and 2.0 Ohm−1 cm−1, respectively. A decrease in the size of the substituent in a series of (BEDT-TTF)2[8,8′-X2-3,3′-Co(1,2-C2B9H10)2] and (BMDT-TTF)4[8,8′-X2-3,3′-Co(1,2-C2B9H10)2] (X = I, Br, Cl) results in the compression of the anion sublattice of the crystal and compaction of the radical cation packing of the conducting layer, which, in turn, increases the conductivity of the crystals.

Methods for the manufacture of nonmetallic reference specimens that are used in liquid-penetrant inspection that allow one to produce flaws with an opening width of up to 1 μm are reported.

A new 2′-deoxyuridine modification, 3′,5′-bis-(dimethyl-tert-butylsilyl)-5-(3-(2-(dimethylamino)ethoxy)-3-methylbutyn-1-yl)-2′-deoxyuridine was effectively synthesized in four easy steps. Its reactivity toward a range of cyclic oxonium adducts of closo-dodecaborate and cobalt-bis-dicarbollide boron clusters was studied. The cleavage reactions of cluster oxonium rings by the N,N-dimethylamino group of the modified nucleoside led to 5-ethynyl-2′-deoxyuridine conjugates with [B12H12]2− and [Co(C2B9H11)2]−, respectively. Cytotoxicity of these new conjugates in several cell lines was examined. Closo-dodecaborate conjugates showed low cytotoxicity in all examined cell lines, an advantageous and preferred property for potential boron delivering drugs for the boron neutron capture therapy (BNCT) of tumors.

New hetero-substituted charge-compensated cobalt bis(1,2-dicarbollide) derivatives were synthesized by the reaction of 8,8′-μ-iodo-3-commo-3-cobalta-bis(1,2-dicarba-closo-dodecaborane) [8,8′-μ-I-3,3′-Co(1,2-C2B9H10)2] with 1,4-thioxane, pyridine N-oxide, and tetrahydropyran. X-ray diffraction studies showed that the 8′-iodo-8-(pyridiniumoxy)eucosahydro-1,1′,2,2′-tetracarba-3-commo-cobalta-closo-tricosaborate molecule has the gauche-conformation (the substituents are turned with respect to each other by 69.2°). The positive charge is predominantly localized on the N(Py) atom.

Conjugates of polyhedral boron hydrides with deoxyadenosine were synthesized by the opening of cyclic oxonium derivatives of closo-dodecaborate and cobalt bis(1,2-dicarbollide) with 2′-deoxyadenosine derivatives containing a nucleophilic group in the substituent at C(8). Biological studies of the derivatives obtained for cytotoxicity revealed that the derivatives based on closo-dodecaborate did not exhibit cytotoxicity. The conjugates obtained can be used in further biological trials as potential agents for boron neutron capture therapy of cancer.

An approach to the synthesis of new 1,4-disubstituted 1,2,3-triazoles, in which one or both substituents contain the cobalt bis(1,2-dicarbollide) fragment, was suggested based on the 1,3-dipolar cycloaddition of azides to alkynes catalyzed by copper(I) compounds. The reaction of cobalt bis(1,2-dicarbollide) azido derivatives with different terminal acetylenes led to 1,2,3-triazoles with the [((CH2)2X(CH2)2O-C2B9H10)Co(C2B9H11)] (X = O or CH2) substituent at position 1 and the organic substituent at position 4. The [3+2] cycloaddition reaction of cobalt bis(1,2-dicarbollide) alkynyl derivatives with methyl azidoacetate furnished isomeric 1,4-disubstituted 1,2,3-triazoles with the metallacarborane fragment at position 4. 1,2,3-Triazole with metallacarborane substituents at positions 1 and 4 containing 36 boron atoms was also synthesized.

Check samples and test panels are used to quality assessment and comparing sensitivity of sets of penetrant material. Authors made research in field of manufacturing non-metal test-objects with specified parameters, such as length a width. The paper considers a technique to determine the depth of blind closed cracks in check samples and non-metal test panels for penetrant inspection with a special tool to measure the depth of the undercut depth or a gauge indicator on the outboard support.

Versions of check sample manufacturing for penetrant inspection are considered. A statistical analysis of crack width measuring for nonmetallic samples is performed to determine the possibility of their application to assess the penetrant testing sensitivity.

Reactions of the iodonium derivative of cobalt bis(dicarbollide) anion [μ-8,8′-I-3,3′-Co(1,2-C2B9H10)2] with activated aromatics were studied. The reactions with ortho- and meta-xylenes result in mild arene C–H activation under ambient conditions, whereas the reaction with para-xylene requires the presence of PPh3 as soft Lewis base. The obtained aryl derivatives [8-Ar-8′-I-3,3′-Co(1,2-C2B9H10)2]− were found to have the transoid conformation both in the solid state and in solution due to intramolecular hydrogen CHcarb⋯IB bonds and aromatic CHcarb⋯π interactions between the dicarbollide ligands. The Lewis acidity of the quasi-borinium cation formed on the breakage of the iodonium bridge was estimated using Beckett–Gutmann method. According to the Gutmann acceptor number AN = 112 (in CD2Cl2), this quasi-borinium cation belongs to the most strong boron Lewis acids and can be considered as Lewis superacid.

A new approach to synthesis of hetero-substituted derivatives of cobalt bis(1,2-dicarbollide) was proposed. The approach involves stepwise introduction of functional groups into different dicarbollide ligands. Halogenation of the monohydroxy derivative [8-OH-3,3′-Co-(1,2-C2B9H10)(1′,2′-C2B9H11)]− gave the corresponding halogen hydroxy derivatives [8-OH-8′-X-3,3′-Co(1,2-C2B9H10)2]− (X = Cl, Br, and I). Reactions of 8,8′-μ-iodonium-3-commo-cobaltbis(1,2-dicarba-closo-dodecaborate) [8,8′-I-3,3′-Co(1,2-C2B9H10)2] with chloroform and 1,2-dibromoethane yielded the mixed halides [8-Y-8′-I-3,3′-Co(1,2-C2B9H10)2]− (Y = Cl and Br).

New 2′-deoxyadenosine and adenosoine modifications: 8-[(2-dimethylaminoethyl)amino]-2′-deoxyadenosine and 8-[(2-dimethylaminoethyl)amino]adenosine were prepared and their reactivity towards cyclic oxonium adducts of closo -dodecaborate and cobalt-bis-dicarbollide was studied. The cleavage reactions of clusters oxonium rings by N , N -dimethylanio group of modified nucleosides led to the first [B 12 H 12 ] 2− and new [Co(C 2 B 9 H 11 ) 2 ] − conjugates with adenosine and 2′-deoxyadenosine respectively. The proposed methodology provides a convenient route for the synthesis of libraries of boron cluster modified adenosine and 2′-deoxyadenosine derivatives for biological screening.

Molecular conductors based on the 8-hydroxy cobalt bis(dicarbollide) anion, (TMTTF)[8-HO-3,3'-Co(1,2-C2B9H10)(1',2'-C2B9H11)] (1), (BMDT-TTF)[8-HO-3,3'-Co(1,2-C2B9H10) (1',2'-C2B9H11)] (2), and (BEDT-TTF)[8-HO-3,3'-Co(1,2-C2B9H10)(1',2'-C2B9H11)] (3), were synthesized, and their crystal structures and electrical conductivities were determined. Compounds 2 and 3 are isostructural to the corresponding radical-cation salts of the parent cobalt bis(dicarbollide). All of the radical-cation salts prepared were found to be semiconductors. The relative stability of the rotation conformers of the [8-HO-3,3'-Co(1,2-C2B9H10)(1',2'-C2B9H11)](-) anion was estimated using DFT/BP86 quantum chemical calculations.

A novel approach to the synthesis of boron-containing amino acids based on ring opening of cyclic oxonium derivatives of polyhedral boron hydrides under the action of the terminal functional groups of natural amino acids was proposed. This approach was successfully implemented for the synthesis of cobalt bis(dicarbollide) — tyrosine conjugate.

Reactions of the iodonium derivative of cobalt bis(dicarbollide) anion [μ-8,8′-I-3,3′-Co(1,2-C2B9H10)2] with Lewis bases in aromatic solvents were studied. The reactions proceed through the iodoniu...

Boron neutron capture therapy (BNCT) is one of the new and promising methods for cancer treatment. 1—4 The further development of this method is inseparably associ� ated with the design of new boroncontaining drugs that can selectively accumulate in the tumor tissue. Amino ac� ids, peptides, nucleotides, and some other molecules trop� ic to tumors can be used as molecules performing the tar� geted boron transport to the tumor. The ability of porphy� rins to be accumulated in cancer cells is well known. This ability in combination with the photoinduced generation of reactive oxygen species makes it possible to use them as photosensitizers in anticancer photodynamic therapy (PDT). 5—7 Photosensitizers based on natural chlorophylls with the enhanced tropicity to tumors, low toxicity, and an intense absorption in the nearIR spectral region, provid� ing the laser radiation action on deeply localized layers of cancer tissues, are of special interest. Therefore, synthesis of conjugates of polyhedral boron compounds with natural porphyrins is a topical issue. 8—16 The porphyrin fragment in these compounds provides the transportation of the bo� roncontaining conjugate to cancer cells and a possibility of visualization of the tumor. The subsequent irradiation of the cells with thermal neutrons and their interaction with the 10 B isotope of boron compounds selectively accu� mulated in cancer cells should result in the selective de� struction of malignant neoplasms. In the present work, the Sonogashira reaction, which is actively employed in modern organic chemistry, 17,18 was used for the synthesis of boroncontaining conjugates of natural porphyrins.

TTF, TTF-BMDT, TTF-BEDT and TMTSF cation radical salts of cobalt bis(dicarbollide) anion [3,3′-Co(1,2-C2B9H11)2]− and its derivatives are prepared and their crystal structures and electrical conductivities are determined. Some regularities in the crystal structures of the TTF-based radical cation salts prepared are also discussed.

Symmetrically substituted dimercuro-ferracarborane commo-(3-Fe-{1,2-C2B9H9-4-SMe2-12-HgCl}2) (1) was synthesized and its structure was determined by single crystal X-ray diffraction. The molecule adopts a staggered sandwich structure with the dicarbollide ligands forming cisoid conformation. Strong intermolecular interactions Hg…C1 and S…Cl lead to formation of 1D chains {commo-(3-Fe-{1,2-C2B9H9-4-SMe2-12-HgCl}2)}∞.

Conjugates of chlorin e6 with closo-dodecaborate and cobalt bis(dicarbollide) anions were synthesized for the first time in high yields using the advanced ‘click’ methodology. In vitro study on A549 human lung adenocarcinoma cells revealed that the synthesized boronated conjugates are able to penetrate and accumulate in cancer cells, but their intracellular concentration is not sufficient for effective photodynamic and boron neutron capture therapy of cancer. Copyright © 2009 John Wiley & Sons, Ltd.

New molecular conductors on the base of 8,8′-diiodo cobalt bis(dicarbollide) anion (TTF)[8,8′-I2-3,3′-Co(1,2-C2B9H10)2] (1), (BMDT-TTF)4[8,8′-I2-3,3′-Co(1,2-C2B9H10)2] (2) and (BEDT-TTF)2[8,8′-I2-3,3′-Co(1,2-C2B9H10)2] (3) were synthesized and their crystal structures and electrical conductivities were determined. All the radical cation salts prepared were found to be semiconductors. Some regularities in the crystal structures of the TTF-based radical cation salts with bis(dicarbollide) complexes of transition metals are discussed.

Conjugates of bacteriochlorin p and chlorin e(6) with cobalt bis(dicarbollide) anion [3,3'-Co(1,2-C(2)B(9)H(11))(2)](-) were synthesized using different synthetic approaches. The boronated bacteriochlorin p was prepared by reaction of bacteriochlorin N-amino cycloimide with, bis(dicarbollide)-based carboxylic acid. The boronated chlorin e(6) conjugates were obtained by both "click reaction" of containing alkyne group chlorine with azide derivative of cobaltacarborane and reaction of chorin-based amines with cyclic oxonium derivative of cobalt bis(dicarbollide).

New radical cation salts (BEDT-TTF)2[3,3′-Co(1,2-C2B9H11)2] (1), (BEDT-TTF)2[8-I-3,3′-Co(1,2-C2B9H10)(1′,2′-C2B9H11)] (2), (BMDT-TTF)[3,3′-Co(1,2-C2B9H11)2] (3) and (TMTSF)2[3,3′-Fe(1,2-C2B9H11)2] (4) were synthesized and their crystal structures and electrical conductivities were determined. Compound 4 is isostructural to the earlier reported Co analogue. All the radical cation salts synthesized are semiconductors.

A new approach to synthesis of functional derivatives of 7,8-dicarba-nido-undecaborate anion based on ring-opening of its cyclic oxonium derivatives [10-(CH2)4O-7,8-C2B9H11] and [10-O(CH2CH2)2O-7,8-C2B9H11] with various nucleophiles was developed. Both cyclic oxonium derivatives can be obtained as single isomers by reaction of the parent anion [7,8-C2B9H12]- with mercury(II) chloride in the corresponding solvents. Mechanism of formation of the cyclic oxonium derivatives of 7,8-dicarba-nido-undecaborate anion was proposed. A series of 7,8-dicarba-nido-undecaborate derivatives with terminal carboxylic and azide functions were prepared by the ring-opening reactions of the cyclic oxonium derivatives with substituted phenolate and azide ions, respectively.

Data on substitution reactions at boron atoms in 10–12-vertex metallacarboranes, which are of fundamental and applied significance, are generalised. The possible mechanisms of substitution reactions and the influence of the metal fragment on substitution positions in the polyhedron are discussed. The bibliography includes 161 references.

New radical cation salt of bis(ethylenedithio)tetrathiafulvalenium and iron bis(dicarbollide) [BEDT-TTF] 2 [3,3′-Fe(1,2-C 2 B 9 H 11 ) 2 ] ( 1 ) has been synthesized. The crystal structure of 1 has been determined by single-crystal X-ray diffraction method found to be isostructural to the known Co and Cr analogues. The electric conductivity measurement in the range of 110 ÷ 296 К shows that 1 is semiconductor with the room temperature conductivity σ 293 = 1.5 × 10 −2 Ω −1 cm −1 , that is higher than in the Cr analogue and lower than in the Co analogue. The measurement of magnetic susceptibility in the range of 2 ÷ 300 K revealed that 1 is paramagnetic with the absence of significant interactions between the organic radical cations and the paramagnetic anions.

The electrophilic mercuration of 3-(η 5 -Cp)-4-SMe 2 -3,1,2-FeC 2 B 9 H 10 ( 1 ) was investigated. The reaction of 1 with the excess of mercury trifluoroacetate in dichloromethane at 20 °C gives complexes containing from two to four substituents depending on the ratio of reagents. All new compounds were separated and characterized by elemental analysis and NMR spectra. The positions of substitution were established by 11 B-NMR and 11 B- 11 B COSY NMR spectra. X-ray structure of 3-(η 5 -Cp)-4-SMe 2 -7,8-(CF 3 COO) 2 -12-HgCl-3,1,2-FeC 2 B 9 H 7 was determined.

The reaction of exo-nido-ruthenacarborane exo-nido-5,6,10-[Cl(Ph3P)2Ru]-5,6,10-(μ-H)3-10-H-7,8-C2B9H8 (1) with the 8-trifluoroacetoxymercury derivative of ferracarborane 3-(η5-Cp)-4-SMe2-8-CF3COOHg-3,1,2-FeC2B9H9 (2) was studied. It was demonstrated for the first time that metallacarborane 2 can be used as a mercurating agent. The reaction afforded 5",6",10"-exo-nido-[Cl(Ph3P)2Ru]-5",6",10"-(μ-H)3-10"-{3-(η5-Cp)-4-SMe2-3,1,2-FeC2B9H9-8-Hg}-7",8"-C2B9H8 (3) existing as two isomers. The structure of trans isomer 3a was established by X-ray diffraction analysis.

8-Tetrahydrofuronium and 8-tetrahydropyronium derivatives of iron bis(dicarbollide)(-I) were synthesized. Their reactions of ring cleavage by MeOH, N3(-), amines and 1,2-bis(diphenylphosphino)ethane were investigated. 8-Tetrahydrofuronium iron bis(dicarbollide)(-I) was found to be more active in these reactions in comparison with 8-tetrahydropyronium and 8-dioxonium species, respectively. The first conjugates of iron bis(1,2-dicarbollide)(-I) with 2'-deoxyadenosine modified via the C-8 position of the purine base were synthesized. Reactions of these oxonium compounds with 1,2-bis(diphenylphosphino)ethane (dppe) led to zwitter-ionic monophosphonium salts. One of these compounds has given rise to a novel ferracarborane/cobaltacarborane hybrid complex.

Bromination and mercuration of cobaltacarborane 1,2,4-CpCoC2B8H10 were investigated. Mercuration under mild conditions (Hg(OCOCF3)2 in CH2Cl2) afforded the only monomercurated complex containing the mercury atom at position 6. Bromination gave rise to 3-mono-, 6-mono-, or 6,9-disubstituted derivatives depending on the reaction conditions. The mercurated derivative was studied by the X-ray diffraction method.

Mercuration and bromination reactions of ferracarborane 3-(η5-Cp)-4-SMe2-3,1,2-FeC2B9H10 (1) were investigated. Mercuration of 1 under mild conditions (mercury trifluoroacetate in dichloromethane) results in 8-monosubstituted mercury derivative as the only reaction product. Depending on the reaction conditions, bromination of 1 results in 8-mono- or 7,8-disubstituted bromo derivatives. The structures of the monomercury and dibromo derivatives of 1 were established by X-ray analysis.

Symmetrical mercury derivative of exo - nido -ruthenacarborane was prepared by two routes: mercuration of exo - nido -5,6,10-[Cl(Ph 3 P) 2 Ru]-5,6,10-(μ-H) 3 -10-H-7,8-C 2 B 9 H 8 ( 1 ) and interaction of Ru(PPh 3 ) 3 Cl 2 with [10,10′-Hg-(7,8-C 2 B 9 H 11 ) 2 ]Cs 2 . Using o -carboran-9-ylmercury trifluoroacetate for mercuration of 1 leads to an unsymmetrical mercury compound with 9- o -carboranyl and exo - nido -ruthenacarboranyl ligands: 5′,6′,10′- exo - nido -[Cl(Ph 3 P) 2 Ru]-5′,6′,10′-(μ-H) 3 -10′-(1,2-C 2 B 10 H 11 Hg-9)-7′,8′-C 2 B 9 H 8 ( 4 ). The same compound was prepared by the action of Ru(PPh 3 ) 3 Cl 2 on [9,10′-Hg-(1,2-C 2 B 10 H 11 )(7′,8′-C 2 B 9 H 11 )]Cs ( 5 ). Both types of new compounds were obtained as a mixture of cis / trans isomers which were separated and characterized by elemental analysis and NMR spectra. The X-ray structure of trans -5′,6′,10′- exo - nido -[Cl(Ph 3 P) 2 Ru]-5′,6′,10′-(μ-H) 3 -10′-(1,2-C 2 B 10 H 11 Hg-9)-7′,8′-C 2 B 9 H 8 ( 4b ) was determined.

The reaction of exo-nido-5,6,10-[Cl(PPh3)2Ru]-5,6,10-(μ-H)3-10-H-7,8-C2B9H8) (1) with [(η4-diene)RhCl]2 in EtOH or with [(CO)2RhCl]2 in MeOH in the presence of KOH produced novel mixed-metal bimetallacarboranes (η4-diene)Rh(μ-H)Ru(PPh3)2(η5-C2B9H11) (4, diene = COD; 5, diene = NBD) or (CO)(PPh3)Rh(μ-H)Ru(PPh3)2(η5-C2B9H11) (10) along with a small amount of the mononuclear complexes closo-(CO)2(PPh3)Ru(η5-C2B9H11) and closo-(CO)(PPh3)2Ru(η5-C2B9H11), respectively. Complexes 4 and 10 were characterized by single-crystal X-ray diffraction studies which revealed the existence of two types of bridging bonds Ru−H−Rh and B−H···Rh in these species. The bridging hydrogen atoms are asymmetrically disposed within these linkages. Several separate experiments have been carried out for the synthesis of the anionic complex [closo-3,3-(PPh3)2-3-H-3,1,2-RuC2B9H11]-, which is proposed to be the key intermediate in the reaction of 1 with [(η4-diene)RhCl]2. The reaction of (PPh3)3RuHCl with [7,8-C2B9H12][Me3NH] under reflux ...