Methyltrioxorhenium and its applications in olefin oxidation, metathesis and aldehyde olefination

Organorhenium(VII) oxides, most notably methyltrioxorhenium (MTO) and several of its derivatives gained significant importance as extremely versatile catalysts for olefin oxidation reactions, aldehyde olefination, olefin metathesis, etc. MTO is nowadays available by several straightforward synthetic procedures and found even applications in material sciences, forming the first known polymeric organometallic oxide. In this review, the applications of MTO in oxidation catalysis, olefin metathesis and aldehyde olefination are summarized and conclusions concerning possible future applications of organorhenium oxides and related complexes are drawn.     

A review on multi-component green synthesis of N-containing heterocycles using mixed oxides as heterogeneous catalysts

The use of mixed oxides is a well-appreciated approach in the fields of material science and synthesis, due to remarkable tunable surface properties such as acidic and basic characteristics, oxidation/reduction capabilities, and high agility of lattice oxygen, which makes them ideal choices as heterogeneous catalysts. The activity of the mixed oxides broadly relies on the nature of support and active material used and on the preparation method, calcination temperatures. Wide range of techniques for preparation of mixed oxide materials are adoptable, viz. sol-gel, co-precipitation, wet impregnation, microwave irradiation and hydrothermal methods. Use of mixed oxides as solid catalysts have gained popularity in many valued organic transformations, via alkylation, oxidation, condensation, dehydration, dehydrogenation, cycloaddition and isomerization. Application of mixed oxides in the area of green organic synthesis is a valuable strategy, which contributed significantly to the design of many novel heterocyclic scaffolds. The chemistry of N-heterocycle scaffolds, which generally possess five and six membered rings, is an interesting area for both synthetic and medicinal chemistry research constituting over 60% organics used in various arenas. The position and number of nitrogen atoms in the rings, distinguish them as pyrroles, pyrazoles, imidazoles, triazoles, pyridines and pyramidines classes. In this review, we focus on the scope, importance and versatile applications of mixed metal oxides and their synergetic effects as heterogeneous catalysts in the synthesis of variety of N-heterocyclic derivatives. The scientific aspects of the mixed oxides as catalytic active materials to design efficient synthetic protocols for the organic transformations is also discussed.     

Oxidation of dodecane on transition metal oxides

The catalytic oxidation of dodecane on individual and mixed vanadium and molybdenum oxides is studied. Products of the oxidation of alkane are studied qualitatively and quantitatively. The activities of the samples of the catalysts with various ratios of vanadium and molybdenum oxides are compared. One possible scheme for the activation of reagents on a catalyst is given.     

Design and synthesis of porous non-noble metal oxides for catalytic removal of VOCs

The design and synthesis of highly active non-noble metal oxide catalysts, such as transition- and rare-earth-metal oxides, have attracted significant attention because of their high efficiency and low cost and the resultant potential applications for the degradation of volatile organic compounds(VOCs). The structure-activity relationships have been well-studied and used to facilitate design of the structure and composition of highly active catalysts. Recently, non-noble metal oxides with porous structures have been used as catalysts for deep oxidation of VOCs, such as aromatic hydrocarbons, aliphatic compounds, aldehydes, and alcohols, with comparable activities to their noble metal counterparts. This review summarizes the growing literature regarding the use of porous metal oxides for the catalytic removal of VOCs, with emphasis on design of the composition and structure and typical synthetic technologies.     

Catalytic oxidative carboncarbon bond cleavage of ketones with dioxygen: assessment of some metal complexes. Some alternatives for preparing α, ω-dicarboxylic acids

This account considers the catalytic oxidative cleavage of ketones with dioxygen. It can be brought about by Keggin-type heteropolyanion complexes containing molybdenum and vanadium as well as by several transition metal catalysts (V(IV, V), Cu(I, II), Fe(III), Ce(IV), etc.), instead of using stoichiometric oxidation with periodate, lead tetra-acetate, etc. Benzylic ketones, ArCH₂C(O)R are oxidised to ArCHO and the corresponding carboxylic acid in high yield at room temperature by dioxygen in the presence of Cu(II) or heteropolyacids H_3+n[PMo_12−nV_nO₄₀]_aq. Although some oxovanadium complexes will induce such oxidations, the heteropolyacids are better, probably due in part to their Brønsted acidity and ability to take part in a variety of equilibria. Treatment of substituted cycloalkanones with a catalytic amount of ‘H₅[PMo₁₀V₂O₄₀]·n H₂O’ (or Cu(II) complexes) under an O₂ atmosphere gives keto-acids in good yield. The selectivities observed at high conversions with various ketones and diols, coupled with the mild conditions and inexpensive oxidant, would seem to make these methods attractive for use in fine chemical manufacture. The scope of these complexes as selective oxidation catalysts can be further extended by associating several metal ions. Such catalysts are being developed for organic synthesis at both the laboratory and industrial scale. Alternative routes to adipic acid involving cyclohexanone, cyclohexene, cyclohexane, etc. and polyoxo(peroxo)metalates or redox molecular sieves as liquid-phase oxidation catalysts, are compared. Alternatives, both biochemical and chemical, are being sought.     

How to synthesize a constrained geometry catalyst (CGC) - A survey

Since the discovery of titanium- and zirconium complexes with linked cyclopentadienyl amido ligands, this new polymerization catalyst class (constrained geometry catalysts “CGCs”) has attracted the interest of many research groups in industry and academia. In order to improve or modify the catalytic and polymer properties, numerous changes in the environment of the catalyst have produced a huge family of CGCs. The aim of this contribution is to provide a concise overview on synthetic entries to these structurally highly diverse catalysts - an organometallic guide to CGCs.     

Degradation of the Pt-MoO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> composite catalyst in methanol solutions

Pt-MoO _x deposits synthesized by an electrochemical method are shown to be instable in methanol solutions at potentials ≥0.3 V. It is assumed that molybdenum oxides in the deposit composition react with methanol. The reduction of molybdenum compounds with methanol to form soluble Mo(+3) complexes in the presence of platinum is confirmed by spectrophotometric data. The MoO _x reaction with methanol leads to the removal of molybdenum compounds from the electrode surface, which is accompanied by the loss of its catalytic activity in the methanol oxidation reaction.     

Metal nature effect on catalytic reactions in furfural-H2O2-H2O-group V or VI d-metal salt systems in acid media

Homogeneous catalytic reactions of furfural oxidation by hydrogen peroxide in an aqueous medium in the presence of catalytic amounts of a vanadium, niobium, molybdenum, or chromium salt have been studied to compare them with the acid-autocatalytic reaction. The formation of peroxo complexes of the corresponding metals has been established. The interaction of these peroxo complexes with the carbonyl group of furfural affords organic metal-containing peroxides. The subsequent transformations of these peroxides in the presence of the indicated catalysts lead to different dominant final products. This is explained by different mechanisms of the oxidation of the key intermediates, namely, 2-formyloxy- and 2-hydroxyfurans. In the presence of the vanadium and molybdenum salts, the catalytic role of the resuting carboxylic acids is insignificant, as distinct from what is observed in the acid-autocatalyzed reaction.

     

Effects of Cerium Oxides on the Catalytic Performance of Pd/CNT for Methanol Oxidation

The carbon nanotubes supported palladium(Pd/CNT)nanocatalysts were modified by cerium oxides/ hydroxides and their catalytic performances for methanol oxidation were evaluated.Electrochemical measurements indicate that the introduction of cerium remarkably improves the catalytic activity of Pd/CNT catalysts towards methanol oxidation.X-Ray photoelectron spectra results reveal an interaction between palladium and cerium oxides.It is also observed that cerium-modified catalysts have excellent poison resistances,which is attributed to the poison-removal ability of cerium oxides/hydroxides.The highly oxidized cerium oxides/hydroxides have a strong ability to inhibit the accumulation of carbonaceous intermediates on the active sites of Pd catalysts.     

Indenylmetal Catalysis in Organic Synthesis

Synthetic organic chemists have a long‐standing appreciation for transition metal cyclopentadienyl complexes, of which many have been used as catalysts for organic transformations. Much less well known are the contributions of the benzo‐fused relative of the cyclopentadienyl ligand, the indenyl ligand, whose unique properties have in many cases imparted differential reactivity in catalytic processes toward the synthesis of small molecules. In this Review, we present examples of indenylmetal complexes in catalysis and compare their reactivity to their cyclopentadienyl analogues, wherever possible.     

Preparation of supported metal catalysts starting from hydrotalcites as the precursors and their improvements by adopting “memory effect”

Hydrotalcite-like compounds (HTlcs) can be used as the catalysts as it is since they contain various transition metal cations as the catalytically active species well dispersed on the basic support materials. Moreover, increasing numbers of the applications of HTlcs after the heat treatment have been found since the oxides with very small crystal size, stable to thermal treatments, are obtained after the calcination. The oxides possess interesting properties such as high surface area, basic properties and further form small and thermally stable metal crystallites by reduction. Moreover, the calcined oxides show a unique property, i.e., “memory effect,” which allows the reconstitution of the original hydrotalcite structure. We have developed the catalytic applications of hydrotalcites as it is and moreover the mixed oxides derived from hydrotalcites for various catalytic reactions, i.e., oxidation, dehydrogenation and reforming of hydrocarbons, and even for the reforming of methanol and the CO shift reaction. Aerobic oxidation of alcohols, Baeyer−Villiger oxidation of ketones and O₃ oxidation of oxalic acid have been successfully carried out with the Mg−Al hydrotalcites containing Ni, Fe and Cu, respectively, as the catalysts in liquid phase. In the O₃ oxidation of oxalic acid, the catalytic activity was enhanced by the “memory effect,” i.e., Mg(Cu)–Al hydrotaclite was reconstituted on the surface of Mg(Cu,Al)O periclase particles and oxalic acid was incorporated as anions in the hydrotalcite layer, resulting in an enhanced oxidation of oxalic acid. As the catalysts in the vapor phase reactions, Mg/Fe/Al mixed oxides prepared from Mg–Al(Fe) hydrotalcites and effectively catalyzed the dehydrogenation of ethylbenzene. Supported Ni metal catalysts have been prepared from Mg(Ni)–Al hydrotalcites and successfully used in the steam reforming and the oxidative reforming of methane and propane. Moreover, the Ni catalysts have been improved by combining a trace amount of noble metals by adopting the “memory effect” and used in the production of hydrogen for the PEFC under the daily startup and shutdown operation. Also starting from aurichalcite or hydrotalcite precursor as the precursor, Cu/Zn/Al catalysts with high Cu metal surface area have been prepared and successfully applied in the steam reforming of methanol and dimethyl ether, and moreover in the CO shift reaction.     

The Effect of Substituents on Catalytic Performance of <Emphasis Type="Italic">bis</Emphasis>-Thiosemicarbazone Mo(VI) Complexes: Synthesis and Spectroscopic,Electrochemical, and Functional Properties

The preparation, characterization and electrochemical properties are reported for three new types of molybdenum(VI) complexes with bis-thiosemicarbazone ligands. All compounds were characterized by elemental analysis, electronic spectra, IR and ¹H NMR spectroscopies, thermogravimetric analysis, and cyclic voltammetry. The bis-thiosemicarbazone Mo(VI) complexes were tested as a catalyst for the homogeneous oxidation of olefins using tert-butyl hydrogen peroxide as an oxidant. The catalysts showed efficient reactivity in the olefins epoxidation reactions giving high yield and selectivity of the products, in most cases. Results showed that the bis-thiosemicarbazone ligands introduced both electronic and steric effects on catalytic performance of the prepared Mo(VI) complexes.     

A general synthetic strategy for oxide-supported metal nanoparticle catalysts

Despite recent exciting progress in catalysis by supported gold nanoparticles, there remains the formidable challenge of preparing supported gold catalysts that collectively incorporate precise control over factors such as size and size-distribution of the gold nanoparticles, homogeneous dispersion of the particles on the support, and the ability to utilize a wide range of supports that profoundly affect catalytic performance. Here, we describe a synthetic methodology that achieves these goals. In this strategy, weak interface interactions evenly deposit presynthesized organic-capped metal nanoparticles on oxide supports. The homogeneous dispersion of nanoparticles on oxides is then locked in place, without aggregation, through careful calcination. The approach takes advantage of recent advances in the synthesis of metal and oxide nanomaterials and helps to bring together these two classes of materials for catalysis applications. An important feature is that the strategy allows metal nanoparticles to be well dispersed on a variety of oxides with few restrictions on their physical and chemical properties. Following this synthetic procedure, we have successfully developed efficient gold catalysts for green chemistry processes, such as the production of ethyl acetate from the selective oxidation of ethanol by oxygen at 100 degrees C.     

Nanocast mesoporous mixed metal oxides for catalytic applications

Since the initial discovery of ordered mesoporous silica in early 1990s, considerable innovations were achieved regarding their synthesis, characterization and applications. One of the best outcomes of these intense research efforts is the development of a solid templating method called “nanocasting”, which is based on using mesoporous silica (or carbon) as a rigid template. This solid-to-solid replication method opened the pathway for synthesizing high surface area non-silica mesostructured materials that are challenging to obtain through conventional self-assembly processes which are based on amphiphilic soft structure-directing agents. In particular, the replicated metal oxide mesostructures obtained by this method were found to be highly versatile for a wide range of applications, especially in catalysis, owing to their large specific surface area. Furthermore, the nanocasting method is particularly suited for the synthesis of mixed metal compositions, favored by the possible confinement of mixed precursors in the nanopores of the template. In this account, we discuss some of the recent developments regarding the synthesis of nanocast mixed metal oxides and their perspectives of catalytic applications. It is here the choice of the authors to place emphasis on a few representative examples of compositions (e.g., non-noble metal-based catalysts, perovskites) and catalytic reactions (e.g., hydrogen production, gas-phase oxidation).     

Hydrogenation of polystyrene‐b‐polybutadiene‐b‐polystyrene mediated by group (IV) metal metallocene complexes

Various group (IV) metal complexes, namely bis(cyclopentadienyl) titanium dichloride, bis(pentamethylcyclopentadienyl) titanium dichloride, cyclopentadienyl titanium trichloride, pentamethylcyclopentadienyl titanium trichloride, bis(cyclopentadienyl) zirconium dichloride, and bis(cyclopentadienyl) hafnium dichloride, were used as the catalysts for mediating styrene–butadiene–styrene hydrogenation. The catalytic efficiency of these catalysts was examined. The results show that catalyst activity strongly depends on the chemical structure of the metallocene complex. We also found that trialkylaluminum has a significant influence on the hydrogenation activity and thermal stability of metallocene catalysts. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2141–2149     

Metallophthalocyanine-based molecular materials as catalysts for electrochemical reactions

Metallophthalocyanines confined on the surface of electrodes are active catalysts for a large variety of electrochemical reactions and electrode surfaces modified by these complexes can be obtained by simple adsorption on graphite and carbon. However, more stable electrodes can be achieved by coating their surfaces with electropolymerized layers of the complexes, that show similar activity than their monomer counterparts. In all cases, fundamental studies carried out with adsorbed layers of these complexes have shown that the redox potential is a very good reactivity index for predicting the catalytic activity of the complexes. Volcano-shaped correlations have been found between the electrocatalytic activity (as log I at constant E) versus the Co(II)/(I) formal potential (E°′) of Co-macrocyclics for the oxidation of several thiols, hydrazine and glucose. For the electroreduction of O₂ only linear correlations between the electrocatalytic activity versus the M(III)/M(II) formal potential have been found using Cr, Mn, Fe and Co phthalocyanines but it is likely that these correlations are “incomplete volcano” correlations. The volcano correlations strongly suggest that E°′, the formal potential of the complex needs to be in a rather narrow potential window for achieving maximum activity, probably corresponding to surface coverages of an M-molecule adduct equal to 0.5 and to standard free energies of adsorption of the reacting molecule on the complex active site equal to zero. These results indicate that the catalytic activity of metallophthalocyanines for the oxidation of several molecules can be “tuned” by manipulating the E°′ formal potential, using proper groups on the macrocyclic ligand. This review emphasizes once more that metallophthalocyanines are extremely versatile materials with many applications in electrocatalysis, electroanalysis, just to mention a few, and they provide very good models for testing their catalytic activity for several reactions. Even though the earlier applications of these complexes were focused on providing active materials for electroreduction of O₂, for making active cathodes for fuel cells, the main trend in the literature nowadays is to use these complexes for making active electrodes for electrochemical sensors.     

The influence of hydrogen-containing molybdenum and tungsten bronzes on the catalytic activity of palladium composite catalysts for the oxidation of H<Subscript>2</Subscript>, CO,and CH<Subscript>4</Subscript>

The influence of hydrogen-containing molybdenum and tungsten bronzes on the catalytic activity of palladium composite catalysts for the oxidation of H₂, CO, and CH₄ was studied. It was found that the composite catalysts containing H _x MO₃ phases (M = W or Mo), which were formed by the reduction of MoO₃ and WO₃ oxides with hydrogen in the presence of deposited Pd, showed higher catalytic activity in the oxidation of small molecules (H₂, CO, and CH₄) with excess oxygen than the traditional Pd/Al₂O₃ deposited catalyst with the same content of the deposited metal. It was shown that the thermal stability of the H _x MO₃ phases was the limiting factor influencing the activity of these composite catalysts.     

Struktur und katalytische Eigenschaften von Molybdänoxid-Trägerkatalysatoren bei einigen Oxydationsreaktionen

Structure and Catalytic Properties of Molybdenum Oxide Supported Catalysts in Some Oxidation Reactions Molybdenum supported catalysts were prepared by using different precursor compounds such as Mo(π-C₃H₅)₄, [Mo(OC₂H₅)₅]₂, MoCl₅, (NH₄)₆Mo₇O₂₄, and their catalytic behaviour in some oxidation reactions was studied. During the preparation process, as a result of interaction between the molybdenum compound used and the support, different surface compounds with strongly differing catalytic properties have been formed. MoO₃ and supported catalysts with MoO₃ crystallites on the surface, catalyse the H₂ oxidation at temperatures above 400°C and the CO oxidation at temperatures of about 500°C. The reaction proceeds according to a redox mechanism. On surface compounds of molybdenum which exist on the surface if organic complexes are used as precursors, the catalytic H₂ oxidation occurs even at 100°C with a high reaction rate. The catalytic CO oxidation on these catalysts occurs at temperatures of about 300°C. An associative mechanism on coordinative unsaturated Mo^VI sites is discussed.     

甘油的催化选择氧化

综述了近年来生物柴油主要副产物甘油的催化选择氧化的研究进展。分析了甘油的化学催化选择氧化的反应网络;介绍了催化甘油选择氧化反应主要的催化剂如负载型金属催化剂、多孔催化剂以及有机酰基-TEMPO催化剂的催化性能及其催化机理;评述了甘油催化氧化过程中各反应条件等对产物选择性和反应物转化率的影响;概括了甘油的电催化氧化、甘油催化氧化聚合生成新型聚合物-聚丙酮二酸盐（Polyketomalonate）等新催化反应及其机理,总结了甘油生物催化氧化的产物二羟基丙酮（DHA）的新进展。最后提出了甘油的催化氧化存在的一些问题,并展望了甘油催化氧化的研究和发展方向。     

Molecular complexes in water oxidation: Pre-catalysts or real catalysts

Artificial photosynthesis is considered a promising method to produce clean and renewable energy by sunlight. To accomplish this aim, development of efficient and robust catalysts for water oxidation and hydrogen production is extremely important. Owing to the advantages of easily modified structures and traceable catalytic processes, molecular water oxidation catalysts (WOCs) attract much attention during the past decade. However, the transformation of molecular WOCs to metal oxides/hydroxides or metal ions may occur under the harsh catalytic conditions, making the identification of true active species difficult. In this article, recent progress on molecular complexes acting as real catalysts or precursors toward water oxidation was briefly reviewed. We summarized the commonly used physical techniques and chemical methods that enable to distinguish homogeneous catalysts from heterogeneous catalysts. The factors that affect the nature of WOCs, such as reaction conditions, transition metal centers, and supporting ligands were discussed as well.