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Nikolaev Institute of Inorganic Chemistry

Siberian Branch of Russian Academy of Sciences

SELECTED RESULTS OF COMPLETED RESEARCH STUDIES in 2013

Content:

    Synthesis and luminescemt properties of the first octahedral molybdenum cluster with six terminal acetylenide ligands

    First octahedral high valence cluster, coordinated uniquely to six carbon atoms (of methylpropyolate), [Mo6I8(C≡CC(O)OMe)6]2−, has been obtained. The cluster exhibits a long-living and bright red luminescence. The presence of reactive triple bond in the propiolate opens new possibilities for modifications of the ligand environment, including making of luminescent dendrimers and incorporation of the luminescent cluster core into polymeric matrices. Such luminescent complexes are of practical interest for design of new generation of sensor materials and farmaceuticals (conversion of triplet O2 molecules into singlet for killing cancer cells), for experimental cytology and histology (as luminescent markers of different sites in cells and tissues)

    Synthesis and luminescemt properties of the first octahedral molybdenum cluster with six terminal acetylenide ligands

    Synthesis and luminescemt properties of the first octahedral molybdenum cluster with six terminal acetylenide ligands

    Sokolov M.N., Mikhailov M.A., Brylev K.A., Virovets A.V., Vicent C., Kompankov N.B., Fedin V.P.Inorg. Chem. 2013. 12477. IF 4,593

    Stabilization of Tetrahedral P4 and As4 Molecules as Guests in Polymeric and Spherical Environments

    [Ag(η2-As4)2]+[pftb] can be used to store yellow arsenic (As4). From it, As4 can be easily released to give concentrated, light-stable solutions. These As4 solutions, and those of white phosphorus (P4), allowed molecular As4 and P4 to be encapsulated inside giant, spherical aggregates and polymeric matrices, enabling the first determination of their E–E (E=P, As) bond lengths by diffraction methods.

    Stabilization of Tetrahedral P4 and As4 Molecules as Guests in Polymeric and Spherical Environments

    Stabilization of Tetrahedral P4 and As4 Molecules as Guests in Polymeric and Spherical Environments

    Schwarzmaier C., Schindler A., Heindl C., Scheuermayer S., Peresypkina E.V., Virovets A.V., Neumeier M., Gschwind R., Scheer M.Angew. Chem. Int. Ed. 2013, 52, 10896. IF = 13,734

    Kinetic factors in the synthesis of silver nanoparticles in reverse micelles of Triton N-42

    For the first time in situ quantitative research of the growth kinetics of silver nanoparticles during the reduction of Ag+ by hydrazine in the reverse micelles of Triton N-42 was carried out. The mechanism of the process includes two steps that are slow, continuous nucleation and fast, autocatalytic surface growth. The parameters as concentration of N2H4 and NH3 as competing ligand, ionic strength and the background salt of dispersed aqueous phase, micelle size, and temperature can be used to regulate the rates of nucleation and autocatalytic surface growth of nanoparticles to provide control synthesis of particles. Silver nanoparticles with definite size and shape are widely used in electronics, catalysis, and biomedicine.

    Kinetic factors in the synthesis of silver nanoparticles in reverse micelles of Triton N-42

    Kinetic factors in the synthesis of silver nanoparticles in reverse micelles of Triton N-42

    Tatarchuk V.V., Sergievskaya A.P., Korda T.M., Druzhinina I.A., Zaikovsky V.I.Chem. Mater., 2013, 3570. IF 8.238

    Unique reactivity of lanthanocenes as a special approach to the polypnictide complexes containing 3d/4f elements

    The NIIC SB RAS research group has been honored by placing the picture of their work to the cover of the prestigious chemical journal Chem. Comm. (IF = 6.378). This work consists in a novel synthetic approach to polypnictide heterometallic complexes of 3d/4f elements. Samarocenes were shown to reveal the unique reactivity towards polyphosphide complexes of 3d/4f elements. The first reductive coupling of polyphosphide complex with P–P bond formation was observed in the reaction of pentaphosphaferrocene and samarocenes. Thereby the pathway to polypnictide polynuclear complexes containing 3d/4f elements as potential molecular pnictide and polypnictide precursors of photo- and thermoelectric materials has been found.

    Unique reactivity of lanthanocenes as a special approach to the polypnictide complexes containing 3d/4f elements

    Unique reactivity of lanthanocenes as a special approach to the polypnictide complexes containing 3d/4f elements

    Li T., Gamer M.T., Scheer M., Konchenko S.N., Roesky P.W.Chem. Commun. 2013. 2183. IF 6.378

    Electron density redistribution in the core region of metal atoms in the course of chemical reactions

    While studying inversion of lead phthalocyanine and methane’s C–H bond activation by palladium atom within the quantum chemical topology it was found that in the course of chemical reactions involving metal compounds a reorganization in the system of metal’s ELF core basins characterizing by the sequence of topological catastrophes occurs. A results obtained are shed some light on the participation of non-valent electrons of the metal in the electronic structure changes of reacting systems.

    Electron density redistribution in the core region of metal atoms in the course of chemical reactions

    Electron density redistribution in the core region of metal atoms in the course of chemical reactions

    Nizovtsev A.S. Kozlova S.G.J. Phys. Chem. A. 2013. V. 117. P. 481. IF= 2.771

    Nizovtsev A.S.J. Comput. Chem. 2013. V. 34. P. 1917. IF= 3.835.

    The synthesis of optically transparent and hard coatings from tetramethyldisilazane

    Silicon carbonitride films were obtained by plasma enhanced chemical vapor decomposition using a gaseous mixture of helium and a volatile organosilicon compound 1,1,3,3-tetramethyldisilazane (TMDS) in the temperature range 373–973 K. The simulation of the deposition process of solid phase mixtures using initial gaseous mixture (TMDS + He) inr the temperature range of 300–1300 K and pressures R0total = 10−2–10 showed the possibility of varying the equilibrium composition of the condensed phases according to the synthesis temperature and initial gaseous mixture composition. Chemical and phase composition, physicochemical, and functional properties of the films obtained in the range 373–973 K were studied by a complex of modern methods: FTIR, Raman, and energy dispersive spectroscopy, X-ray photoelectron spectroscopy, scanning electron and atomic force microscopy, XRD using synchrotron radiation, ellipsometry, spectrophotometry.

    The synthesis of optically transparent and hard coatings from tetramethyldisilazane

    The synthesis of optically transparent and hard coatings from tetramethyldisilazane

    N. I. Fainer, A. N. Golubenko, Yu. M. Rumyantsev, V. G. Kesler, E. A. Maximovskii, B. M. Ayupov, F. A. KuznetsovGlass Physics and Chemistry. 2013. Т. 39, № 1. С. 77–88. IF 0,339

    Synthesis and thermochemical characteristics of BaCe0.7Gd0.2In0.1O2.85 having high stability

    For the first time the barium cerate doped by gadolinium and indium (BaCe0.7Gd0.2In0.1O2.85) having high stability was synthesized by solid state method. Thermochemical characteristics of BaCe0.7Gd0.2In0.1O2.85 phase were determined by solution calorimetry. It was shown that barium cerate doped by gadolinium and indium was thermodynamically stable with respect to decomposition into binary oxides. It was established that compound BaCe0.7Gd0.2In0.1O2.85 is thermodynamically more stable than phases BaCe0.7Nd0.2In0.1O2.85, BaCe0.8Nd0.2O2.9, etc. Barium cerates doped by trivalent elements are perspective proton conductors for application in fuel cells, sensors and ceramic membranes. Increasing of solubility limit by adding of indium increases the quantity of proton defects and stability of compounds. The research is performed in cooperation with Karlsruhe Institute of Technology (Germany) and Institute of Solid State Chemistry of Ural Branch of the Russian Academy of Science.

    Synthesis and thermochemical characteristics of BaCe0.7Gd0.2In0.1O2.85 having high stability

    Synthesis and thermochemical characteristics of BaCe0.7Gd0.2In0.1O2.85 having high stability

    Matskevich N.I., Matskevich M.Yu., Wolf Th., Bryzgalova A.N., Chupakhina T.I., Anyfrieva O.I.J. Alloys Comp. 2013. V.577. P. 148-151. IF = 2.390

    Speciation of Platinum(IV) in Nitric Acid Solutions

    The speciation of platinum(IV) ions in nitric acid solutions (widely used precursor for preparation of heterogeneous catalysts) has been discovered. Series of aqua-hydroxo-nitrato complexes [Pt(L)x(NO3)6−x] (L = H2O or OH; x = 0, ..., 6) were found to exist in the fresh prepared solutions. Aging of the platinum nitric acid solutions for more than 5−6 h results in oligomerization of [Pt(L)x(NO3)6−x] species and the formation of oligonuclear aqua-hydroxo-nitrato complexes with OH bridging ligands. Mononuclear complex [Pt(NO3)6]2– and oligomeric platinum(IV) species with two, four and seven nuclei [Pt2(μ-OH)2(NO3)8]2– , [Pt4(μ-O)2(μ-OH)4(NO3)10]2–, [Pt7(μ-O2)6(μ-OH)6(NO3)12]2– have been isolated as single crystals of salts with organic cations and characterized by X-ray diffraction.

    Mono- and polynuclear species of Pt(IV) in nitric acid solution of H2[Pt(OH)6]

    Mono- and polynuclear species of Pt(IV) in nitric acid solution of H2[Pt(OH)6]

    Vasilchenko D.B., Tkachev S.V, Baidina I.A., Korenev S.V.Inorg. Chem. 2013. 52. 10532. IF 4,593

    Cluster complexes based on the new heterometallic core {Re3Mo3S8}

    A facile way to obtain octahedral heterometallic (Re/Mo) cluster complexes has been developed. Direct synthesis of the K6[Re3Mo3S8(CN)4(CN)2/2] polymeric cluster with the new {Re3Mo3S8} 24-electron core has been realized using the MS2 and KCN as precursors. Dissolution of polymeric compound led to isolation of soluble salt containing stable paramagnetic 23e cluster anion [Re3Mo3S8(CN)6]6–. The cyclic voltammetry revealed a reversible one-electron oxidation wave which corresponds to the 23e/22e oxidation process of the cluster core. The wide ox-red chemistry of the described cluster anions open the way to control properties of their derivatives. Paramagnetic cluster anion [Re3Mo3S8(CN)6]6– is interesting as the component of the magnetoactive inorganic polymers.

    Cluster complexes based on the new heterometallic core {Re3Mo3S8}–

    Cluster complexes based on the new heterometallic core {Re3Mo3S8}

    Gayfulin Y.M., Naumov N.G., Rizhikov M.R., Smolentsev A.I., Nadolinny V.A., Mironov Y.V.Chem. Commun., 2013, 49, 10019. IF 6,378