• CAS Future Leader 2019
  • Mendeleev 2019
  • Старт 53 Международной Менделеевской олимпиаде школьников по химии
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Репрезентативные публикации за январь 2019 г.

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D.V.Zhuzhelskii, E.G.Tolstopjatova, S.N.Eliseeva, A.V.Ivanov, ShouleiMiao, V.V.Kondratiev, Electrochemical properties of PEDOT/WO3 composite films for high performance supercapacitor application, Electrochimica Acta, 2019, V.209, P.182-190. DOI: 10.1016/j.electacta.2019.01.007

Abstract

Tungsten oxide was electrochemically deposited from a metastable acidic solution of isopolytungstate on glassy carbon electrodes coated by the films of a conducting polymer poly-3,4-ethylenedioxythiophene (PEDOT). The formation of PEDOT/WO3 composite films during electrochemical deposition of tungsten oxide into the polymer matrix was gravimetrically monitored by EQCM. The morphology of WO3 deposits was studied using SEM, TEM and EDX analysis, including element mapping and depth concentration profile of main elements. SEM and TEM images of PEDOT/WO3 composites show disperse distribution of WO3 precipitates in the porous matrix of PEDOT, possessing high surface area and pore volume, effective for charge transport. Electrochemical behavior of PEDOT/WO3 was investigated in 0.5 M H2SO4 by cyclic voltammetry, galvanostatic charge-discharge method and electrochemical impedance spectroscopy. The WO3 component in the obtained PEDOT/WO3 composite electrodes exhibited high specific capacitance of 689 F g−1 in the potential range −0.3–0.0 V. The work presents a simple approach for the synthesis of PEDOT/WO3 composites with high values of specific capacitance. The obtained results indicate that PEDOT/WO3 composite could be a promising electrode material for supercapacitor applications.


Anton V. Rozhkov, Mariya A. Krykova, Daniil M. Ivanov, Alexander S. Novikov, Anna A. Sinelshchikova, Marina V. Volostnykh, Mikhail A. Konovalov, Mikhail S. Grigoriev, Yulia G. Gorbunova, Vadim Yurievich Kukushkin, Reverse Arene Sandwich Structures Based upon π‐hole•••[MII] (d8M = Pt, Pd) Interactions, where Positively Charged Metal Centers Play the Role of a Nucleophile, Angew. Chem. Int. Ed., Accepted Author Manuscript. DOI: 10.1002/ange.201814062

Abstract

The complexes [Pt(tpp)] (M = Pt; H2tpp = tetraphenyl‐porphyrin), [M(acac)2] (M = Pd, Pt, Hacac = acetylacetone), and [Pd(ba)2] (Hba = benzoylacetone) were co‐crystallized with highly electron‐deficient arene systems to form reverse arene sandwich structures built by π‐hole•••[MII] (d8M = Pt, Pd) interactions. The adduct [Pt(tpp)]•2C6F6 is monomeric, whereas the diketonate 1:1 adducts form columnar infinity 1D‐stack assembled by simultaneous action of both π‐hole•••[MII] and C–F interactions. The reverse sandwiches are based on noncovalent interactions and calculated ESP distributions indicate that in π‐hole•••[MII] contacts, [MII] plays the role of a nucleophile.


Kamran T.Mahmudov, Vadim Yu.Kukushkin, Atash V.Gurbanova, Mikhail A.Kinzhalov, Vadim P.Boyarskiy, M. Fátima C. Guedesda Silva, Armando J.L.Pombeiro, Isocyanide metal complexes in catalysis, Coordination Chemistry Reviews, 384, 65–89, 2019. DOI: 10.1016/j.ccr.2019.01.002

Abstract

The catalytic applications of isocyanide metal systems (from early to late transition metals) for organic transformations were systematically reviewed, and the studied transformations are also classified by type regardless of the metal center. A broad range of catalytic reactions of organic substrates has been developed including reactions of alkenes and alkynes, functionalization of E–H and E–E to multiple bonds, alkyl- and aryl-halides activation, nucleophilic addition, electron transfer catalysis, and photochemical reactions. This report gives a general overview of reaction routes, mechanisms, and driving forces and highlights the potential of isocyanide metal species, drawing attention to emerging putative targets.