Facile Insertion of Carbon Dioxide into Cu2(μ‐H) Dinuclear Units Supported by Tetraphosphine Ligands

Reactions of meso‐bis[(diphenylphosphinomethyl)phenylphosphino]methane (dpmppm) with Cu^I species in the presence of NaBH₄ afforded di‐ and tetranuclear copper hydride complexes, [Cu₂(μ‐H)(μ‐dpmppm)₂]X ( 1 ) and [Cu₄(μ‐H)₂(μ₄‐H)(μ‐dpmppm)₂]X ( 2 ) (X=BF₄, PF₆). Complex 1 undergoes facile insertion of CO₂ (1 atm) at room temperature, leading to a formate‐bridged dicopper complex [Cu₂(μ‐HCOO)(dpmppm)₂]X ( 3 ). The experimental and DFT theoretical studies clearly demonstrate that CO₂ insertion into the Cu₂(μ‐H) unit occurred with the flexible dicopper platform. Complex 2 also undergoes CO₂ insertion to give a formate‐bridged complex, [Cu₄(μ‐HCOO)₃(dpmppm)₂]X, during which the square Cu₄ framework opened up to a linear tetranuclear chain.     

Hydrogen storage over alkali metal hydride and alkali metal hydroxide composites

Alkali metal hydroxide and hydride composite systems contain both protic(H bonded with O) and hydridic hydrogen. The interaction of these two types of hydrides produces hydrogen. The enthalpy of dehydrogenation increased with the increase of atomic number of alkali metals,i.e.,-23 kJ/molH2 for LiOH-LiH, 55.34 kJ/molH2 for NaOH-NaH and 222 kJ/molH2 for KOH-KH. These thermodynamic calculation results were consistent with our experimental results. H2 was released from LiOH-LiH system during ball milling. The dehydrogenation temperature of NaOH-NaH system was about 150℃; whereas KOH and KH did not interact with each other during the heating process. Instead, KH decomposed by itself. In these three systems, NaOH-NaH was the only reversible hydrogen storage system, the enthalpy of dehydrogenation was about 55.65 kJ/molH2, and the corresponding entropy was ca. 101.23 J/(molH2 K), so the temperature for releasing 1.0 bar H2 was as high as 518℃, showing unfavorable thermodynamic properties. The activation energy for hydrogen desorption of NaOH-NaH was found to be57.87 kJ/mol, showing good kinetic properties.     

Assessment of Hydrocarbon Electron‐Impact Ionization Cross Section Measurements for Magnetic Fusion

Partial ionization cross section experiments have been carried out recently at the University of Innsbruck for three types of hydrocarbons, i.e. acetylene, ethylene and propene. Cross section data fits are generated and compared to the compilation of earlier experimental data summarized in the online database HYDKIN [www.hydkin.de]. New data fits are brought into a suitable form to be incorporated into the database. In order to illuminate underlying dissociation mechanisms the energy dependence of branching ratios above energies of 20 –30 eV is reviewed in light of the present results (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Hydrogenation of Pd-capped Mg thin films prepared by DC magnetron sputtering

Structural and optical properties of pure Mg thin film coated with Pd have been investigated. Pd-capped Mg thin films had been prepared by DC magnetron sputtering. This work presents an ex situ study on hydrogenation and dehydrogenation kinetics of Pd/Mg films at different conditions using XRD, AFM and optical spectrophotometer. We have succeeded to load thin films of Mg to MgH₂ at normal temperature and normal pressure of hydrogen gas. In hydrogenation, α-MgH₂ phase of magnesium hydride was observed in hydrogenated films at 200 °C and γ-MgH₂ at 250 °C respectively. The desorption kinetics in vacuum also revealed the phase transformation α-MgH₂ to γ-MgH₂. A reflectance change was observed in hydrogenated films in comparison of as deposited thin film. Hydrogenated (H loaded) samples were observed partially transparent in comparison of as deposited.     

BeH2材料的制备及在ICF中的应用

 简述了BeH_{2材料的制备方法、结构形式和物理化学性质，并分析了其在惯性约束聚变(ICF)中的应用。BeH2材料主要由二叔丁基铍热解法和元素化学气相沉积法制备，其纯度(质量分数)高达99%。非晶BeH2材料的结构是一种共用氢原子作为顶点的BeH4四面体网络结构。非晶BeH2材料不仅具有铍的优点，还具有聚合物的优点，作为ICF靶可以降低瑞利-泰勒不稳定性，而且掺入高Z元素后还可以降低D-T燃料的预热。非晶BeH2材料作为烧蚀层，掺入高Z元素后可以提高激光-X光的转换效率。}     

Determination of inorganic arsenic and organic arsenic compounds in marine organisms by hydride generation/cold trap/gas chromatography— mass spectrometry

The behavior of arsenite, methylarsonic acid, dimethylarsinic acid, trimethylarsine oxide, dimethyl-R-arsine oxides, and trimethyl-R-arsonium compounds (R = carboxymethyl, 2-carboxyethyl, 2-hydroxyethyl) toward sodium borohydride and hot aqueous sodium hydroxide was investigated. The arsines obtained by sodium borohydride reduction of the undigested and digested solutions were collected in a liquid-nitrogen cooled trap, separated with a gas chromatograph, and detected with a mass spectrometer in the selected-ion-monitoring mode. The investigated arsenic compounds were stable in hot 2 mol dm^?3 sodium hydroxide except arsenobetaine [trimethyl(carboxymethyl)arsonium zwitterion] that was converted to trimethylarsine oxide, and dimethyl(ribosyl)arsine oxides that were decomposed to dimethylarsinic acid. Hydride generation before and after digestion of extracts from marine organisms allowed inorganic arsenic, methylated arsenic, arsenobetaine, and ribosyl arsenic compounds to be identified and quantified. This method was applied to extracts from shellfish, fish, crustaceans, and seaweeds.     

Bioorganometallic chemistry: biocatalytic oxidation reactions with biomimetic NAD/NADH co-factors and [Cp*Rh(bpy)H] for selective organic synthesis

The biocatalytic, regioselective hydroxylation of 2-hydroxybiphenyl to the corresponding catechol was accomplished utilizing the monooxygenase 2-hydroxybiphenyl 3-monooxygenase (HbpA). The necessary natural 1,4-dihydronicotinamde adenine dinucleotide (NADH) co-factor for this biocatalytic process was replaced by a biomimetic co-factor, N-benzyl-1,4-dihydronicotinamide, 1b. The interaction between the flavin (FAD) containing HbpA enzyme and the corresponding biomimetic NADH compound, N-benzyl-1,4-dihdronicotinamide, 1b, for hydride transfer, was shown to readily occur. The in situ recycling of the reduced NADH biomimic 1b from 1a was accomplished with [Cp*Rh(bpy)H](Cl); however, productive coupling of this regeneration reaction to the enzymatic hydroxylation reaction was not totally successful, due to a deactivation process concerning the HbpA enzyme peripheral groups; i.e., -SH or -NH₂ possibly reacting with the precatalyst, [Cp*Rh(bpy)(H₂O)](Cl)₂, and thus inhibiting the co-factor regeneration process. The deactivation mechanism was studied, and a promising strategy of derivatizing these peripheral -SH or -NH₂ groups with a polymer containing epoxide was successful in circumventing the undesired interaction between HbpA and the precatalyst. This latter strategy allowed tandem co-factor regeneration using 1a or 2a, [Cp*Rh(bpy)(H₂O)](Cl)₂, and formate ion, in conjunction with the polymer bound, FAD containing HbpA enzyme to provide the catechol product.     

Asymmetric reduction of acetophenone and propiophenone by NaAl(IPTOLate)H2 combined with enantiomeric enrichment of the reaction product as an inclusion complex with IPTOL

An improved procedure was developed for asymmetric reduction of acetophenone and propiophenone by the chiral reagent NaAl(IPTOLate)H₂. This procedure is based on isolation of the chiral alcohol that formed as a crystalline host—guest complex with the IPTOL ligand. The enantiomeric enrichment of the product was as high as 97% ee. The ability of IPTOL and its analogs to form host—guest complexes with a number of ether-type solvents, 1-phenylethanol, and 1-phenylpropan-1-ol as well as thermal stabilities of IPTOL-containing complexes with these alcohols were studied.     

Activation process in hydrogen storage related to oxide layers formed on zirconium alloys

The passive behavior of ZrNi alloys near the rest potential is studied through in situ voltammetry, ellipsometry, and microscopic observation. A significant oxide layer growth is observed in aqueous 1 M KOH during the application of different potential programs currently used in the activation processes of the alloy. Oxide barrier effects and occlusion of hydrogen species within the film take place. The kinetics of the oxide layer formation under potential cycling plays a significant role in the activation process of metal alloys used in metal hydride batteries.Dedicated to Professor Gyorgy Horanyi on the occasion of his 70th birthday.