Hyper-Cross-Linked Polyacetylene-Type Microporous Networks Decorated with Terminal Ethynyl Groups as Heterogeneous Acid Catalysts for Acetalization and Esterification Reactions.

Heterogeneous catalysts based on materials with permanent porosity are of great interest owing to their high specific surface area, easy separation, recovery, and recycling ability. Additionally, porous polymer catalysts (PPCs) allow us to tune catalytic activity by introducing various functional centres. This study reports the preparation of PPCs with a permanent micro/mesoporous texture and a specific surface area SBET of up to 1000 m2 g-1 active in acid-catalyzed reactions, namely aldehyde and ketone acetalization and carboxylic acid esterification. These PPC-type conjugated hyper-cross-linked polyarylacetylene networks were prepared by chain-growth homopolymerization of 1,4-diethynylbenzene, 1,3,5-triethynylbenzene and tetrakis(4-ethynylphenyl)methane. However, only some ethynyl groups of the monomers (from 58 to 80 %) were polymerized into the polyacetylene network segments while the other ethynyl groups remained unreacted. Depending on the number of ethynyl groups per monomer molecule and the covalent structure of the monomer, PPCs were decorated with unreacted ethynyl groups from 3.2 to 6.7 mmol g-1 . The hydrogen atoms of the unreacted ethynyl groups served as acid catalytic centres of the aforementioned organic reactions. To the best of our knowledge, this is first study describing the high activity of hydrogen atoms of ethynyl groups in acid-catalyzed reactions.

Immobilization of Methyltrioxorhenium on Mesoporous Aluminosilicate Materials.

The presented report focuses on an in-depth detailed characterization of immobilized methyltrioxorhenium (MTO), giving catalysts with a wide spectra of utilization. The range of mesoporous materials with different SiO2/Al2O3 ratios, namely mesoporous alumina (MA), aluminosilicates type Siral (with Al content 60%-90%) and MCM-41, were used as supports for immobilization of MTO. The tested support materials (aluminous/siliceous) exhibited high surface area, well-defined regular structure and narrow pore size distribution of mesopores, and therefore represent excellent supports for the active components. Some of the supports were modified by zinc chloride in order to obtain catalysts with higher activities for instance in metathesis reactions. The immobilization of MTO was optimized using these supports and it was successful using all supports. The success of the immobilization of MTO and the properties of the prepared heterogeneous catalysts were characterized using X-ray Fluorescence (XRF), atomic absorption spectroscopy (AAS), X-ray powder diffraction (XRD), scanning electron microscopy (SEM), physical adsorption of N2, ultraviolet-visible spectroscopy (UV-Vis), infrared spectroscopy (FTIR), Fourier Transform Infrared Spectroscopy (FTIR) using pyridine as a probe molecule and X-ray photoelectron spectroscopy (XPS). Furthermore, the catalytic activity of the immobilized MTO on the tested supports was demonstrated on metathesis reactions of various substrates.

Opportunities offered by chiral η6-arene/N-arylsulfonyl-diamine-RuII catalysts in the asymmetric transfer hydrogenation of ketones and imines.

Methods for the asymmetric transfer hydrogenation (ATH) of ketones and imines are still being intensively studied and developed. Of foremost interest is the use of Noyori's [RuCl(η6-arene)(N-TsDPEN)] complexes in the presence of a hydrogen donor (i-PrOH, formic acid). These complexes have found numerous practical applications and have been extensively modified. The resulting derivatives have been heterogenized, used in ATH in water or ionic liquids and even some attempts have been made to approach the properties of biocatalysts. Therefore, an appropriate modification of the catalyst that suits the specific requirements for the reaction conditions is very often readily available. The mechanism of the reaction has also been explored to a great extent. Model substrates, acetophenone (a ketone) and 6,7-dimethoxy-1-methyl-3,4-dihydroisoquinoline (an imine), are both reduced by this Ru catalytic system with almost perfect selectivity. However, in each case the major product is a different enantiomer (S- for an alcohol, R- for an amine when the S,S-catalyst is used), which demanded an in-depth mechanistic investigation. Full-scale molecular modelling of this system enabled us to visualize the plausible 3D structures of the transition states, allowing the proposition of a viable explanation of previous experimental findings.

The influence of operating conditions on the efficiency of vapor phase hydrogen peroxide in the degradation of 4-(dimethylamino)benzaldehyde.

Vapor phase hydrogen peroxide (VPHP) nowadays finds more and more applications especially as a bio-decontamination agent for enclosed areas. Although this oxidizing agent logically offers a potential for the degradation of hazardous chemical contaminants, the information on the utilization within this area is very limited. The main objective of this study was to examine in detail the influence of basic operational (temperature, concentration of VPHP, relative humidity, condensation) and other conditions (e.g. amount of contaminant, the effect of UV radiation) on the efficiency of the VPHP process for the degradation of the selected model substance, i.e. 4-(dimethylamino)benzaldehyde. For this purpose, a series of different VPHP "wet" decontamination cycles (with a visible condensation) were carried out and compared. The obtained results clearly proved that VPHP could be utilized for the degradation of 4-(dimethylamino)benzaldehyde, however it was necessary to regard this process as a multi-parametric, in which all operational conditions played significant roles, while the molecular distribution of H(2)O and H(2)O(2) at first constituted the key factor for a successful degradation of contaminants on the surface. In order to achieve the highest decomposition efficiency of 4-(dimethylamino)benzaldehyde by the wet VPHP process, it appeared to be necessary to decrease the initial relative humidity in the relevant enclosed area (ideally up to 5%) before the introduction of VPHP and carry out this decontamination procedure ideally at 25°C and maintain the VPHP concentration higher than 500 ppm. Furthermore, it was found that the addition of UV radiation had a positive role on VPHP efficiency (in the best case, the degradation rate increased up to 1.5 times compared to using the sole VPHP). The monitoring of the concentration of VPHP within an enclosed facility is a good tool for the monitoring of the degradation of chemical contaminants by this agent.

The platinum-olefin binding energy in series of (PH3)2Pt(olefin) complexes--a theoretical study.

Theoretical investigation of Pt(0)-olefin organometallic complexes containing tertiary phosphine ligands was focused on the strength of platinum-olefin electronic interaction. DFT theoretical study of electronic effects in a substantial number of ethylene derivatives was evaluated in terms of the Pt-olefin binding energy using MP2 correlation theory. Organometallics bearing coordinated olefins with general formula (R1R2C = CR3R4)Pt(PH3)2 [R = various substituents] had been selected, including olefins containing both electron-donor substituents as well as electron-withdrawing groups. The stability of the corresponding complexes increases with a strengthening electron-withdrawal ability of the olefin substituents.