Organometallic chemistry of 15-membered tri-olefinic macrocycles: catalysis by palladium(0) complexes in carbon-carbon bond-forming reactions

15-Membered macrocycles (E,E,E)-1,6,11-tris(arenesulfonyl)-1,6,11-triazacyclopentadeca-3,8,13-trienes (1) are prepared from arenesulfonamides and trans-1,4-dibromo-2-butene. Macrocycles 1 coordinate palladium(0), platinum(0), and silver(I). The palladium complexes are useful and reutilizable catalysts or precatalysts in Suzuki cross-couplings, butadiene telomerizations, hydroarylation of alkynes, and in the Heck reaction. Structurally related macrocycles are also available by similar synthetic procedures.     

Nanoparticles for catalysis in aqueous media

This review highlights the recent development of nanocatalyst-enabled chemical transformations in water, leveraging the nanomicelle/surfactant chemistry and related technology. Various chemical reactions, including the most frequently used transformations in the pharmaceutical industry, are discussed herein. A potential implementation of such nano-technology in large-scale synthesis at an industry level is also briefly touched on.     

Water-soluble glycodendrimers: synthesis and stabilization of catalytically active Pd and Pt nanoparticles

A new water-soluble glycodendrimer containing 9 terminal modified xylose branches was prepared from nona-azide terminated dendrimer by ‘click’ chemistry. The glycodendrimer was analyzed by ¹H, ¹³C NMR and mass spectroscopy and used to stabilize palladium (PdNPs) and platine (PtNPs) nanoparticles. These DSN are stable in water and were characterized by TEM. The platinum NPs showed a remarkable catalytically activity for olefin hydrogenation in water at room temperature.     

Organostannoxane-supported Pd(0) nanoparticles as efficient catalysts for Heck-coupling reactions

A new functional organostannoxane cage, SnP, that contains phosphine ligands in its periphery has been structurally utilized as support palladium(0) nanoparticles SnPPd. The latter was shown to catalyze the Heck coupling reactions of wide variety of functionalities efficiently.     

When gold is not noble: catalysis by nanoparticles

Bulk gold is chemically inert and is generally regarded as a poor catalyst. However, when gold is in very small particles with diameters below 10 nm and is deposited on metal oxides or activated carbon, it becomes surprisingly active, especially at low temperatures, for many reactions such as CO oxidation and propylene epoxidation. The catalytic performance of Au is defined by three major factors: contact structure, support selection, and particle size. The role of the perimeter interfaces of Au particles as the sites for reactions is discussed as well as the change in chemical reactivity of Au clusters composed of fewer than 300 atoms.     

Recent developments in the application of nanoparticles prepared from w/o microemulsions in heterogeneous catalysis

This paper reviews the use of microemulsions, especially the water-in-oil (w/o) microemulsions, for preparation of nanoparticles that are employed as catalyst components in heterogeneous catalytic reactions. The objective is to show the growing interest of using microemulsions in the preparation of different types of materials such as metals, single metal oxides or mixed metal oxides with a broad range of application in heterogeneous catalysis and also in electrocatalysis. In most cases, the catalytic material showed improved catalytic properties as a result of the special synthesis environment created by the microemulsions. Still, research is needed for a better understanding of such beneficial effects. In addition, this method needs improvements in order to produce, in an environmentally friendly way, a suitable amount of material for use in industrial-scale catalytic processes.     

Mn3O4 nanoplates and nanoparticles: Synthesis, characterization, electrochemical and catalytic properties

Mn₃O₄ hexagonal nanoplates and nanoparticles were synthesized via a solvent-assisted hydrothermal oxidation process at low temperature and a solvothermal oxidation method, respectively. The synthesized product was characterized by powder X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), electron diffraction (ED), Fourier transform infrared (FT-IR) spectroscopy. Their capability of catalytic oxidation of formaldehyde to formic acid at room temperature and atmospheric pressure and electrochemical properties by cyclic voltammogram (CV) were compared. The results showed that Mn₃O₄ hexagonal nanoplate is a better catalyst, and the hexagonal nanoplates and nanoparticles modified electrodes blended with carbon black have a higher specific capacitance.     

Concave Pt-Cu-Fe ternary nanocubes:One-pot synthesis and their electrocatalytic activity of methanol and formic acid oxidation

Concave nanostructures may be developed to improve the specific mass activity of a catalyst for formic acid and methanol electro-oxidation. In this work, we report the elctrocatalytic oxidation of methanol and formic acid in acid medium over concave Pt-Cu-Fe ternary nanocubes (NCs), obtained by the galvanic exchange of Pt and Fe on Cu NCs. The concave Pt-Cu-Fe NCs exhibited improved electrooxidation performance contrasted to Pt-Cu NCs and purchased commercial Pt/C as demonstrated by their improved durability, lower onset potential, and more preferable anti-poisoning properties. These properties are believed to originate from the tailored concave structure of the catalyst and possible synergetic effects among the components of the Pt-Cu-Fe NCs.     

Surfactant-assisted low-temperature thermal decomposition route to spherical NiO nanoparticles

Thermal decomposition has been employed to access spherical nickel oxide (NiO) nanoparticles from a new precursor, nickel-salicylate, [Ni(C₇H₅O₃)₂(H₂O)₄]. Surfactants, triphenylphosphine ((C₆H₅)₃P), and oleylamine (C₁₈H₃₅NH₂) were added to control the particle size. The products were characterized by X-ray diffraction, transmission electron microscopy (TEM), Fourier transform infrared spectroscopy, and thermogravimetric analysis. TEM images showed particles nearly spherical having sizes 5–15?nm. The magnetism of NiO nanoparticles was studied with a vibrating sample magnetometer. Due to smaller particle size and increased surface uncompensated spins, a superparamagnetic behavior is observed. The synthetic process is simple and affords high-purity material at a relatively lower calcination temperature.     

各向异性金纳米粒子的制备及其在催化中的应用

尽管有关金纳米粒子催化的研究工作很多,但其中大多数都是采用传统的浸渍法将金盐负载到载体上、共沉淀或沉积-沉淀法制得负载的纳米粒子,但这些方法并未吸收最新的纳米技术。最近,金催化剂的研究者开发了在胶态悬浮液中制取金属纳米粒子,然后进行固载,从而使得单金属和双金属催化剂的催化活性和形貌控制取得较大进展。另一方面,最近十年出现了金纳米粒子合成的高级控制技术,得到了许多各向异性的金纳米粒子,且很容易制得新的形貌,可以控制纳米粒子的表面原子配位数和光学特性(可调的等离子体带),这些都与催化密切相关。这些形貌包括纳米棒、纳米星、纳米花、树枝状纳米结构或多面体纳米粒子等。除了高度关注各向异性金纳米粒子的最新开发的制备方法和性质,本综述也清楚地总结了这些纳米粒子独特的催化性能,以及通过提供更高催化性能的金催化剂、控制暴露的活性位,以及热、电和光催化的鲁棒性和可调性,从而给多相催化领域带来令人惊奇的潜在变革。     

Sustainable green catalysis by supported metal nanoparticles

The recent progress of sustainable green catalysis by supported metal nanoparticles is described. The template synthesis of metal nanoparticles in ordered porous materials is studied for the rational design of heterogeneous catalysts capable of high activity and selectivity. The application of these materials in green catalytic processes results in a unique activity and selectivity arising from the concerted effect of metal nanoparticles and supports. The high catalytic performances of Pt nanoparticles in mesoporous silica is reported. Supported metal catalysts have also been applied to biomass conversion by heterogeneous catalysis. Additionally, the degradation of cellulose by supported metal catalysts, in which bifunctional catalysis of acid and metal plays the key role for the hydrolysis and reduction of cellulose, is also reported. © 2009 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 9: 224–235; 2009: Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.200900004     

Michael addition of 1,3-dicarbonyl compounds catalyzed by iron oxide nanoparticles

Several iron oxides nanoparticles (Fe₂O₃@Fe₂O₃, Fe°@Fe₂O₃, GO@Fe₂O₃ and calcinated Fe₂O₃) have been assessed as catalysts in the 1,4-addition of a cyclic β-ketoester onto methyl vinyl ketone under neat conditions. It appeared that calcinated Fe₂O₃NP are efficient catalysts at 1?mol% loading for the Michael addition of 1,3-dicarbonyl compounds onto various enones.     

In situ formation of Ni nanoparticles supported on NiFe2O4 by calcination

Ni/NiFe₂O₄ composites have been successfully prepared by calcination at 400°C in air of the mixture K₃[Fe(ox)₃]·2.5H₂O and NiCl₂·6H₂O with a molar ratio of 0.7-2. The products are featured by the Ni crystallite size of 15-34 nm, BET surface area of 23-41 m²/g and variable Ni loadings. TGA and FTIR results indicate in situ generation of CO molecules from decomposition of K₃[Fe(ox)₃]·2.5H₂O. These in situ generated CO molecules account for the formation of Ni nanoparticles by reduction of Ni(II) ions.     

Elimination of β-palladium hydroxide in the Pd-catalyzed reaction of methyl (α-hydroxymethyl)acrylate with alcohols

Exclusive elimination of β-Pd-OH takes place in the oxypalladation intermediate derived from methyl (α-hydroxymethyl)acrylate and alcohols with PdCl₂ catalyst, and no β-Pd-H elimination occurs.     

Supramolecular cluster catalysis: facts and problems

By checking the chemistry underlying the concept of “supramolecular cluster catalysis” we identified two major errors in our publications related to this topic, which are essentially due to contamination problems. (1) The conversion of the “closed” cluster cation [H₃Ru₃(C₆H₆)(C₆Me₆)₂(O)]⁺ (1) into the “open” cluster cation [H₂Ru₃(C₆H₆)(C₆Me₆)₂(O)(OH)]⁺ (2), which we had ascribed to a reaction with water in the presence of ethylbenzene is simply an oxidation reaction which occurs in the presence of air. (2) The higher catalytic activity observed with ethylbenzene, which we had erroneously attributed to the “open” cluster cation [H₂Ru₃(C₆H₆)(C₆Me₆)₂(O)(OH)]⁺ (2), was due to the formation of RuO₂ · nH₂O, caused by a hydroperoxide contamination present in ethylbenzene.     

Size effect in thiol and amine binding to small Pt nanoparticles

A study was carried out to compare the binding affinities of 1-dodecanethiol and dodecylamine for small Pt nanoparticles. The results showed that the affinity of thiol for Pt nanoparticles increases with increasing particle size whereas the affinity of amine for Pt nanoparticles decreases. The divergence in binding affinities has resulted in differences in catalytic activities of thiol- and amine-protected Pt nanoparticles in the room temperature electro-oxidation of methanol (a fuel cell reaction). It was therefore possible for the larger Pt nanoparticles to be catalytically more active than the smaller Pt nanoparticles up to a certain critical size, before the surface area effects of nanoparticles become noticeable.     

Electroanalytical Study of Methanol Oxidation and Oxygen Reduction at Carbon Nanohorns‐Pt Nanostructured Electrodes

This work reports a comprehensive electroanalytical study of carbon nanohorns (CNHs) in electrochemical applications. Compared to other types of carbons, the bare CNHs electrode exhibited higher peak current densities and lowest anodic peak‐to‐cathodic peak separation of less than 50 mV for the [Fe(CN)^4?]₆/[Fe(CN)^3?]₆ redox couple. Furthermore, CNHs exhibited excellent electrocatalyst supporting properties for porous Pt film towards methanol oxidation reaction reaching a peak current density of 127 mA cm^?2 or peak current mass activity 184 mA mg_Pt^?1. Regarding oxygen reduction reaction, an onset potential as positive as 0. 77 V vs. Ag/AgCl was achieved with CNHs/porous Pt film.     

Some chelating C-donor ligands in hydrogen transfer and related catalysis

Recent work is discussed that throws light on synthetic, steric, and electronic aspects of NHC complexes as well as on outer sphere effects in their reactivity. The chemistry of the NHC ligand is much more complex than the more traditional phosphines and provides much greater possibilities for altering steric and electronic properties for tuning reactivity. In synthetic work the Lin Ag₂O method is shown to be inapplicable to the synthesis of abnormal NHCs bound via C-4(5) where the C2 position is blocked with CH₃, because Ag(I) oxidizes the CH₃ group to formate with formation of the normal C-2 bound Ag-NHC. Linker effects on the behavior of chelating NHCs depend on the linker locking the azole rings into a conformation that depends on linker length. This gives rise to different complexes being formed when different linker lengths are employed. The failure of M-NHC bonds to reversibly dissociate can prevent potentially chelating bis and tris NHC precursors from forming the desired products but instead being trapped in a kinetic nonchelate form. Imidazolium carboxylates prove to be synthetically useful in that they can act as excellent NHC transfer agents to a variety of transition metals. The Tolman electronic parameter of NHCs can be determined by a variety of experimental and computational methods. Anion dependent chemistry can give rise to a switching of the product of imidazolium salt metallation from normal (C-2) to abnormal (C-4(5)) forms.     

Ruthenium catalysis in six-membered O-heterocycles synthesis

Due to significant biological activity associated with N-, O-, and S-heterocycles, several reports for their synthesis have appeared in recent decades. Traditional approaches require expensive or highly specialized equipment or would be of limited use to the synthetic organic chemist due to their highly inconvenient approaches. This review summarizes the applications of ruthenium metal with emphasis of their synthetic applications for oxygen-containing six-membered heterocylces. In summary, this review article describes the synthesis of heterocyclic rings containing different heteroatoms.     

金催化CO氧化湿度增强效应的理论研究

实验发现纳米金催化的CO氧化有良好的湿度增强效应,但有关机制仍不清楚.我们应用密度泛函理论研究了湿度增强效应的微观机制,以Au4团簇为例,研究了金催化CO氧化的微观机理,考察了H2O在反应中的角色和作用.计算结果表明,H2O与Au4团簇一样,在反应中扮演催化剂的角色,参与反应的进行、改变反应历程、降低反应能垒.催化循环包含4个基元步骤：O2＋H2O→OOH＋OH,CO＋OOH→CO2＋OH,CO＋OH→COOH,和COOH＋OH→CO2＋H2O,其中自由基OOH和OH的形成是催化循环的速控步骤,其能垒为100.31kJ/mol,明显低于非水参与反应的能垒（161.41kJ/mol）.目前的结果合理地解释了实验观测的CO催化氧化的湿度增强效应,给出了其微观反应机制.