Ternary Alkali Metal Transition Metal Acetylides

The first alkali metal transition metal acetylides of general composition A₂M⁰C₂ (A = Na ? Cs, M⁰ = Pd, Pt) were obtained by solid state reactions of alkali metal acetylides with palladium and platinum. They are characterized by chains, which are separated by alkali metal ions. Analogous chains also separated by alkali metal ions are the characteristic structural feature of acetylides of composition AM^IC₂, which are accessible by reacting AC₂H with M^II in liquid ammonia (A = Li ? Cs, M^I = Cu, Ag, Au). Despite their structural similarities they possess different properties, as acetylides of composition A₂M⁰C₂ are semiconductors with very small indirect band gaps and slightly extended C–C distances compared to a C–C triple bond, whereas acetylides of composition AM^IC₂ show a typical salt‐like behavior with C–C distances close to the expected value for a C–C triple bond of 120 pm. But with the help of simple chemical models these differences can be made plausible. Furthermore, it is shown that only by a combination of different methods (powder diffraction with X‐rays and neutrons, solid state NMR spectroscopy, Raman spectroscopy) it was possible to characterize this new class of compounds structurally and chemically.     

Metal/Metal Redox Isomerism Governed by Configuration

A pair of diastereomeric dinuclear complexes, [Tp′(CO)BrW{μ-η²-C,C′-κ²-S,P-C₂(PPh₂)S}Ru(η⁵-C₅H₅)(PPh₃)], in which W and Ru are bridged by a phosphinyl(thiolato)alkyne in a side-on carbon P,S-chelate coordination mode, were synthesized, separated and fully characterized. Even though the isomers are similar in their spectroscopic properties and redox potentials, the like-isomer is oxidized at W while the unlike-isomer is oxidized at Ru, which is proven by IR, NIR and EPR-spectroscopy supported by spectro-electrochemistry and computational methods. The second oxidation of the complexes was shown to take place at the metal left unaffected in the first redox step. Finally, the tipping point could be realized in the unlike isomer of the electronically tuned thiophenolate congener [Tp′(CO)(PhS)W{μ-η²-C,C′-κ²-S,P-C₂(PPh₂)S}Ru(η⁵-C₅H₅)-(PPh₃)], in which valence trapped W^III/Ru^II and W^II/Ru^III cationic species are at equilibrium.     

One-Pot Synthesis of High-Strained Metal Vinylidene and Metal Carbyne

A novel one-pot reaction producing a metal vinylidene structure in a five-membered ring by cyclization of a multiyne has been achieved. The ring strain and the high stability of the cyclic metal vinylidene complexes have been analyzed experimentally and computationally. The metal vinylidene unit in a fused-ring complex is unreactive to both nucleophiles and electrophiles. It reacts however at the nearby carbonyl group achieving the unprecedented conversion of metal tributing factors for the aromaticity-driven process has been studied by DFT calculations.     

Reactions of Metal Salts and Alkali Metal Nitrates. Role of the Metal Precursors and Alkali Metal Ions in the Resulting Phase of Zirconia

Zirconia powders are prepared by reaction of a zirconium precursor with an alkali metal nitrate. The major part of the reactions takes place before the melting points and then the reactions go slowly to completion at 450°C in the molten salts. The roles of the precursor and the alkali metal ion are discussed considering the reaction between two precursors, octahydrated zirconium oxychloride and zirconium tetrachloride, and two nitrates, LiNO₃ and NaNO₃, and some resulting physico-chemical differences. The obtained zirconia powders contain very small amounts of alkali metal ions which act as stabilizing agent. Their effect on the balance tetragonal-monoclinic ZrO₂ depends upon the homogeneity of their distribution which is related to their ability to diffuse inside the bulk of particles and their polarizing power when located mainly on the surface.     

Electrochemistry of Hydroquinone Derivatives at Metal and Iodine-modified Metal Electrodes

IntroductionPlatinumand gold surfaces can adsorb a wide vari-ety of ions, atoms and molecular functional groups,which is often accompanied by oxidation-reduction ordissociation of them. Numerous previous works havemade great progress in studying the surfa…     

金属和金属氧化物热反应的实验探究

报道了有关金属和金属氧化物之间热反应的实验,经研究发现,一种金属都能在高温下夺取另一种金属性比它弱的金属氧化物中的氧,能够将另一种金属从氧化物中还原出来。     

Metal nanopowder demulsifiers

Metal nanopowders were found to affect the stability of hydrophobic emulsions. A nanoreagent as effective as highly nonionic demulsifiers was found. It can easily be separated and retains its efficiency after repeated use. The mechanisms of the process were discussed.     

含硅金属化合物

近年来,含硅金属化合物由于在催化工业等领域的广泛应用受到了化学工作者的重视.本文综述了以硅原子或硅杂链为配体的桥形成的金属络合物、金属硅氧烷、硅-金属化合物、金属不饱和硅化物和含硅多金属络合物5种含硅金属化合物的研究进展,并对该领域的研究方向提出了展望.     

Metal Nano-Cluster Biosensors

Resonant enhancement of absorptive properties of metal clusters bound to a surface by biorecognitive interactions is an effective means to set up bio-optical devices. Resonant amplification of a four-layer system has been proposed and recently demonstrated with a metal mirror, a polymer distance layer, a biomolecule interaction layer and a sub-monolayer of biorecognitively bound metal nano-clusters. Calculations and corresponding experiments indicated a strong influence of cluster symmetry and cluster shell on the distinct reflection minimum induced by the resonant behavior. Here, we present the first biosensor which clearly shows a narrow reflection minima system in the red or infra-red and therefore far away from the limit exhibited by spherical gold colloids at around 600?nm. The asymmetry of the metal clusters (synthesized by thermal step reduction in a detergent system) as well as metal–dielectric shell clusters (synthesized by multiple shell deposition processes) enabled us to shift the readout of the device to a frequency range where blood is highly transparent. Disposable single step assays were established, employing lectin–sugar, antigen–antibody and protein–receptor interactions.     

金属复合膜

本文介绍了金属膜和金属复合膜在加氢和脱氢反应中的应用及金属复合膜的常用制备方法和发展趋势。与非复合的金属膜相比,金属复合膜具有氢透量高、金属用量少和成本低等优点。     

Nanoporous Metal Foams

Nanoporous metal foams (NMFs) have been a long sought‐after class of materials in the quest for high‐surface‐area conductive and catalytic materials. Herein we present an overview of newly developed synthetic strategies for producing NMFs along with an in‐depth discussion of combustion synthesis as a versatile and scalable approach for the preparation of nanoporous, nanostructured metal foams. Current applications of NMFs prepared using combustion synthesis are also presented including hydrogen storage and catalysis.     

Ligand-Free Metal Clusters

Recent advances in the synthesis and spectroscopic characterization of ligand-free metal clusters immobilized in cryogenic rare gas matrices have contributed greatly to the understanding of electronic, geometric, dynamic, and chemical bonding properties of a wide range of uni- and bimetallic clusters as a function of nuclearity and metal type. The knowledge accumulated on molecular metal aggregates devoid of ligands and isolated on various supports will form an important data base for gauging the reliability of quantum chemical calculations on metal clusters, as well as for comprehending certain aspects of chemisorption on, and catalysis by, supported metal clusters. It can be envisaged that information on ligand-free metal clusters entrapped in a wide range of matrix environments in conjunction with the data for these same metal clusters in the gas phase and in molecular beams will probably contribute towards understanding metal-support interactions and to the designed synthesis of a new breed of high-technology heterogeneous catalysts in the not too distant future.     

金属配位聚氨酯

金属配位聚氨酯(Metal coordination polyurethanes,MCP)是一维配体聚氨酯(Polyurethanes,PU)阵列通过与零维配位中心金属离子或离子簇的配位作用,形成的一维、二维或三维结构的金属有机组装体。这些金属有机组装体既保留有机高分子PU的特征,又兼备无机金属的性能,因而受到国内外研究人员的广泛关注。由于金属与高分子互动产生的超结构凝聚态,可进一步赋予MCP自修复、记忆、抗菌和荧光等特殊功能,从而成为近年来的研究热点之一,但尚未有关于MCP的专题报道。本文从分子组成结构探究PU与金属(碱土金属、过渡金属、稀土金属和其他金属)相互作用的途径与方法,阐述其微观结构与宏观性能的关联,并对MCP功能材料的发展和应用做出展望。 Coordination of carboxylate, sulphonate, pyridine, Schiff base, and other groups in ligand polyurethanes with metal ions or ionic clusters to prepare metal coordination polyurethanes     

Condensed Metal Clusters

The chemistry of metals in low valence states is marked by the frequent occurrence of metal clusters, which are easily recognizable when they occur as molecular units. Many metal-rich compounds of transition metals with p-elements (3rd to the 6th main groups) are closely related to the corresponding halides, since they are built up from metal clusters of the same type. The clusters are however, linked together (condensed) by metal-metal bonds. This principle of construction holds particularly well in the case of the novel reduced halides of the lanthanoids.     

Rare-Earth Metal Methanephosphonates

Addition of a KOH solution to aqueous solutions containing methanephosphonic acid H₂L andrare-earth ions Ln^{3 +} results in crystallization of LnHL₂ (Ln = La-Er, Y), KLn3H6L8 (Ln = Yb, Lu); Tmforms the salts of both types. The solubility and thermal stability of the products were studied.