Reactions of [HOs3(CO)8{µ3-Ph2PCH(R)P(Ph)C6H4}] (R = H,Me) with Bu3SnH: synthesis and structure of bimetallic Os-Sn clusters

Reactions of unsaturated [HOs₃(CO)₈{µ₃-Ph₂PCH(R)P(Ph)C₆H₄}] (R?=?H, Me) with Bu₃SnH are examined. [HOs₃(CO)₈{µ₃-Ph₂PCH(R)P(Ph)C₆H₄}] reacts with Bu₃SnH at room temperature to afford [H₂Os₃(CO)₈(SnBu₃){µ₃-Ph₂PCH(R)P(Ph)C₆H₄}] (1) via oxidative addition of the Sn?H bond to the parent cluster. Heating 1 in refluxing toluene leads to the formation of [H₂Os₃(CO)₇(SnBu₃){µ₃-Ph₂PCH(R)P(Ph)C₆H₄}] (2) through decarbonylation. Cluster 2 exists in two isomeric forms in solution which has been probed by VT NMR spectroscopy. The new Os-Sn bimetallic clusters have been characterized by a combination of analytical and spectroscopic data together with single-crystal X-ray diffraction analysis.

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First Synthesis of Continuous Mesoporous Copper Films with Uniformly Sized Pores by Electrochemical Soft Templating

Although mesoporous metals have been synthesized by electrochemical methods, the possible compositions have been limited to noble metals (e.g., palladium, platinum, gold) and their alloys. Herein we describe the first fabrication of continuously mesoporous Cu films using polymeric micelles as soft templates to control the growth of Cu under sophisticated electrochemical conditions. Uniformly sized mesopores are evenly distributed over the entire film, and the pore walls are composed of highly crystalized Cu.     

Networks of periodic orbits in the circular restricted three-body problem with first order post-Newtonian terms

The motivation of this article is to numerically investigate the orbital dynamics of the planar post-Newtonian circular restricted problem of three bodies. By numerically integrating several large sets of initial conditions of orbits we obtain the basins of escape. Additionally, we determine the influence of the transition parameter on the orbital structure of the system, as well as on the families of simple symmetric periodic orbits. The networks and the stability of the symmetric periodic orbits are revealed, while the corresponding critical periodic solutions are also identified. The parametric evolution of the horizontal and the vertical stability of the periodic orbits are also monitored, as a function of the transition parameter.

     

Studies on thermal degradation of acrylonitrile–butadiene–styrene copolymer (ABS-Br) containing brominated flame retardant

The thermal degradation of acrylonitrile-butadiene-styrene copolymer (ABS-Br; 10 g) containing brominated flame retardant (Br: 9.59 wt.%) was carried out at 450 °C using a semi batch operation using two different temperature programs. The heating rate was found to affect the quality of the degradation oil and yield of products (liquid, gas and residue). Data on the effect of the temperature program on the accumulation of liquid products was presented. It was found that the majority of the bromine was concentrated in the carbon residue and while majority of the nitrogen accumulates in the liquid products irrespective of degradation mode. The use of a one step constant heating rate process (I) produced a higher liquid yield (39%), than a two step process (29%). Differences were also noted in the Br and N contained in the liquids produced by the two processes.     

Reactor production of anhydrous18F ion

The direct production of anhydrous¹³F ion has been achieved through the incorporation of a new approach to hot atom reactions for reactor generated radiopharmaceuticals. Capitalizing on the traditional Li₂CO₃ method for hydrated¹⁸F production, a unique target design and geometry utilizing neutron generated energetic tritions emerging from the surface of a thin LiF embedded stainless steel matrix react with gaseous O₂ to produce¹⁸F as a free recoiling anhydrous species. Approximately 10–15 MBq of reactive anhydrous¹⁸F ion absorbed onto a metallic foil has been produced by this method. Verification of the production of¹⁸F was substantiated through decay measurements using Ge(Li) spectroscopic analysis, and by the synthesis of¹⁸F-fluoromethane gas. Cyclotron gas target chemistry which has been instrumental in the preparation of¹⁸F-2FDG and other metabolic tracers may be reproduced using this technique by the addition of 1% F₂ scavenger gas to a recirculating reactor gas handling system.     

Synthesis of Chiral Ionic Polymers Containing Quaternary Ammonium Sulfonate Structure and their Catalytic Activity in Asymmetric Alkylation

Repeated reaction between chiral quaternary ammonium dimer and disodium disulfonate gave the ionic polymer, which contains chiral quaternary ammonium sulfonate structure as a repeating unit. This chiral ionic polymer showed an excellent catalytic activity in asymmetric alkylation reaction. With the chiral ionic polymer catalysts, high level of enantioselectivities up to 97% ee were attained.     

Transamidation of Amides and Amidation of Esters by Selective N–C(O)/O–C(O) Cleavage Mediated by Air- and Moisture-Stable Half-Sandwich Nickel(II)–NHC Complexes

The formation of amide bonds represents one of the most fundamental processes in organic synthesis. Transition-metal-catalyzed activation of acyclic twisted amides has emerged as an increasingly powerful platform in synthesis. Herein, we report the transamidation of N-activated twisted amides by selective N–C(O) cleavage mediated by air- and moisture-stable half-sandwich Ni(II)–NHC (NHC = N-heterocyclic carbenes) complexes. We demonstrate that the readily available cyclopentadienyl complex, [CpNi(IPr)Cl] (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene), promotes highly selective transamidation of the N–C(O) bond in twisted N-Boc amides with non-nucleophilic anilines. The reaction provides access to secondary anilides via the non-conventional amide bond-forming pathway. Furthermore, the amidation of activated phenolic and unactivated methyl esters mediated by [CpNi(IPr)Cl] is reported. This study sets the stage for the broad utilization of well-defined, air- and moisture-stable Ni(II)–NHC complexes in catalytic amide bond-forming protocols by unconventional C(acyl)–N and C(acyl)–O bond cleavage reactions.     

Micellization and Clouding Phenomenon of Phenothiazine Drug Promethazine Hydrochloride: Effect of NaCl and Urea Addition

Herein we report the micellization and clouding behavior of promethazine hydrochloride (PMT) in absence and presence of NaCl/ureas. The critical micelle concentration (CMC) of PMT is measured by conductivity method and the values decrease with increasing the NaCl concentration. With increasing the temperature, the CMC first increases then decreases. At 25°C, the maximum CMC values were obtained (with or without NaCl). The thermodynamic parameters are evaluated which indicate more stability of the PMT solution in presence of NaCl. PMT shows phase separation also. The cloud point (CP) of PMT decreases with increase in pH due to deprotonation of the drug molecules. Ureas decreased the CP and the behavior is explained on the basis of removal of water from the head group region.     

Infrared Spectroscopic Analysis of Chrysene and 1.2-Benzanthracence in Wax films

Chrysene and 1.2-benzanthracene are successfully doped in a solid wax film and their vibrational spectra in gooo--400cm^-1 are discussed. The harmonic frequencies and relative intensities of both the molecules observed in the film are compared with theoretical values calculated by the density functional theory （DFT） model as well as with the previous experimental data. The effects on spectra due to change of matrix and some additional bands observed in the wax film are also reported. Excellent agreement in the spectral positions and strengths between the experiments and DFT values are found.     

Electronic phase separation in transition metal oxide systems

Electronic phase separation is increasingly getting recognized as a phenomenon of importance in understanding the magnetic and electron transport properties of transition metal oxides. The phenomenon dominates the rare-earth manganates of the formula Ln(1-x)A(x)MnO(3)(Ln = rare earth and A = alkaline earth) which exhibit ferromagnetism and metallicity as well as charge-ordering, depending on the composition, size of A-site cations and external factors such as magnetic and electric fields. We discuss typical phase separation scenarios in the manganates, with particular reference to Pr(1-x)Ca(x)MnO(3)(x= 0.3-0.4), (La(1-x)Ln(x))(0.7)Ca(0.3)MnO(3)(Ln = Pr, Nd, Gd and Y) and Nd(0.5)Sr(0.5)MnO(3). Besides discussing the magnetic and electron transport properties, we discuss electric field effects. Rare-earth cobaltates of the type Pr(0.7)Ca(0.3)CoO(3) and Gd(0.5)Ba(0.5)CoO(3) also exhibit interesting magnetic and electron transport properties which can be understood in terms of phase separation.