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161.
Redox and Coordination Behavior of the Hexaphosphabenzene Ligand in [(Cp*Mo)2(μ,η6:η6‐P6)] Towards the “Naked” Cations Cu+, Ag+, and Tl+
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Martin Fleischmann Fabian Dielmann Laurence J. Gregoriades Eugenia V. Peresypkina Alexander V. Virovets Sebastian Huber Alexey Y. Timoshkin Gbor Balzs Manfred Scheer 《Angewandte Chemie (International ed. in English)》2015,54(44):13110-13115
Although the cyclo‐P6 complex [(Cp*Mo)2(μ,η6:η6‐P6)] ( 1 ) was reported 30 years ago, little is known about its chemistry. Herein, we report a high‐yielding synthesis of 1 , the complex 2 , which contains an unprecedented cyclo‐P10 ligand, and the reactivity of 1 towards the “naked” cations Cu+, Ag+, and Tl+. Besides the formation of the single oxidation products 3 a,b which have a bisallylic distorted cyclo‐P6 middle deck, the [M( 1 )2]+ complexes are described which show distorted square‐planar (M=Cu( 4 a ), Ag( 4 b )) or distorted tetrahedral coordinated (M=Cu( 5 )) M+ cations. The choice of solvent enabled control over the reaction outcome for Cu+, as proved by powder XRD and supported by DFT calculations. The reaction with Tl+ affords a layered two‐dimensional coordination network in the solid state. 相似文献
162.
Hydrogen Storage Materials: Room‐Temperature Wet‐Chemistry Approach toward Mixed‐Metal Borohydrides
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Dr. Tomasz Jaroń Piotr A. Orłowski Wojciech Wegner Dr. Karol J. Fijałkowski Dr. Piotr J. Leszczyński Prof. Wojciech Grochala 《Angewandte Chemie (International ed. in English)》2015,54(4):1236-1239
The poor kinetics of hydrogen evolution and the irreversibility of the hydrogen discharge hamper the use of transition metal borohydrides as hydrogen storage materials, and the drawbacks of current synthetic methods obstruct the exploration of these systems. A wet‐chemistry approach, which is based on solvent‐mediated metathesis reactions of precursors containing bulky organic cations and weakly coordinating anions, leads to mixed‐metal borohydrides that contain only a small amount of “dead mass”. The applicability of this method is exemplified by Li[Zn2(BH4)5] and M[Zn(BH4)3] salts (M=Na, K), and its extension to other systems is discussed. 相似文献
163.
Reactions of Polyarsenides with Acetylene: Synthesis and Characterization of [Cs([18]crown‐6)]2As7C14H11·6NH3 and As2C6H6
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The reaction of Cs3As7 with diphenylacetylene in the presence of 18 crown‐6 in liquid ammonia results in the formation of the new compound [Cs( 18 crown‐6)]2As7C14H11 · 6NH3, which crystallizes in black monoclinic crystals. It contains the first monosubstituated heptaarsenide anion with a hydrocarbon‐only substituent and theoretical calculations show a significant influence of the organic substituent on the electronic structure within the cage. The (Z)‐1, 2‐diphenylethenyl‐heptaarsenide di‐anion can be seen as the first step towards the formation of 1, 2,3‐triarsolides. Further experiments regarding the reaction of Rb3As11 and Cs3As11 with acetylene gas in liquid ammonia reveal the formation of the diarsabarrelene As2C6H6, which crystallizes as colorless orthorhombic crystals. Calculations based on the structural data obtained by X‐ray crystallography show the electronically inert character of the arsenic lone pair. 相似文献
164.
Stability and Conversion of Tin Zintl Anions in Liquid Ammonia Investigated by NMR Spectroscopy
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Franziska Fendt Dr. Carina Koch Dr. Maria Neumeier Dr. Stefanie Gärtner Prof. Dr. Ruth M. Gschwind Prof. Dr. Nikolaus Korber 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(41):14539-14544
Homoatomic polyanions of post‐transition main‐group metals, namely, Zintl anions, are precast in analogous Zintl phases and can react in solution to form new materials. Despite comprehensible reaction approaches, the formed products cannot be planned in advance, as hitherto undetected and therefore disregarded side reactions take place. The outcomes and interpretations of the reactions of Zintl anions are so far based mainly on crystal structures, which only allow characterization of the product that has the lowest solubility. Here we present the results of our investigation of the stability of highly charged tin Zintl anions in liquid ammonia, which is not exclusively based on solution effects but also on the oxidative influence of the solvent. This allows for a deeper understanding of the ongoing processes in solution and opens doors to the directed synthesis of transition metal complexes of Sn44?, here shown by its reactivity towards MesCu. 相似文献
165.
Frontispiece: New Dual Fluorescent Probe for Simultaneous Biothiol and Phosphate Bioimaging
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166.
Inside Back Cover: A Multifunctional Bimetallic Molecular Device for Ultrasensitive Detection,Naked‐Eye Recognition,and Elimination of Cyanide Ions (Chem. Eur. J. 37/2015)
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167.
离子液体作为一种新型绿色环保有机化合物,因具有饱和蒸气压低、溶解性良好以及电导率高等优异性质,而在化学化工领域中得到了较为广泛的应用,并越来越受到人们的关注。该文综述了近年来离子色谱在离子液体阴阳离子分析中的应用,对离子色谱法分析离子液体阳离子、离子液体阴离子以及同时分析离子液体阴阳离子三方面进行讨论,并对离子色谱法分析离子液体的发展趋势进行了展望。 相似文献
168.
169.
P.K. Sazonov Z. D?ambaskiM.M. Shtern R. Markovi?I.P. Beletskaya 《Tetrahedron letters》2011,52(1):29-33
Bromophilic attack by the transition metal carbonyl anion, [Re(CO)5]Na (pKa = 21.1), on 2-(1-bromoalkylidene)thiazolidin-4-ones is significantly faster than abstraction of an acidic lactam hydrogen (pKa ∼17-18), when the generated carbanion is stabilized by an α-CN or α-PhCO group. The bromophilic reaction of 2-(1-bromoalkylidene)thiazolidin-4-one, having an α-CN electron-withdrawing group, resulted in formation of a new metallacyclic anionic complex. With less reactive vinyl bromides, containing an α-CONHPh or α-CO2Et group, only deprotonation is observed. The role of the metal carbonyl anion is highlighted by a comparison with the 9-methylfluorenide carbanion (pKa of 9-methylfluorene is 22.3), which reacts exclusively via a deprotonation pathway. 相似文献
170.
Melting reactions of copper, CuI, selenium, and Bi2Se3 yielded black, shiny needles of Cu4BiSe4I = Cu4BiSe2(Se2)I. The compound decomposes peritectically above 635(5) K and crystallizes in the orthorhombic space group Pnma with a = 960.1(1) pm, b = 413.16(3) pm, and c = 2274.7(2) pm (T = 293(2) K). In the crystal structure, strands ${1}\atop{{\infty}}$ [BiSeSe2/2(Se2)2/2]3– run along [010]. Therein, the bismuth(III) cation is coordinated by five selenium atoms, which form a square pyramid. The copper(I) cations are coordinated tetrahedrally by selenide, diselenide and iodide ions. Edge‐sharing of these tetrahedra results in zigzag chains of copper cations with short distances of 262.7(4) pm. Enhanced dispersion of the 3d bands, the Crystal Orbital Hamilton Populations (COHP), and disynaptic ELI‐D basins indicate weakly attractive d10···d10 interactions between the copper cations. The semiconducting properties and the calculated electronic band structure suggest an electron‐precise compound. In copper‐deficient Cu3.824(8)BiSe4I, the Cu···Cu distances are 5 pm shorter, and Raman spectroscopy indicates the presence of diselenide(1–) radical anions besides the diselenide(2–) groups. As a result, in Cu3.824(8)BiSe4I, selenium coexists in the oxidations states –II, –I, and –0.5. 相似文献