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H2 Gas (h2 + gas)
Selected AbstractsSynthesis of Ruthenium Hydride Complexes Containing beta-Aminophosphine Ligands Derived from Amino Acids and their use in the H2 -Hydrogenation of Ketones and IminesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 4 2005Kamaluddin Abdur-Rashid Abstract The new complexes RuHCl(PPh2CH2CHRNH2)2 and RuHCl(PPh2CH2CHRNH2)(R- binap), R=H (Pgly), R=Me [(R)-Pala] were prepared by the substitution of the PPh3 ligands in RuHCl(PPh3)3 or RuHCl(PPh3)[(R)-binap] with beta-aminophosphines derived from amino acids. The complex trans -RuHCl(Pgly)[(R)-binap] has been characterized by X-ray crystallography. The complex trans -RuHCl[(S)-Ppro]2 where (S)-Ppro is derived from proline was also prepared and characterized by X-ray crystallography. These were used as catalyst precursors in the presence of a base (KOPr- i or KOBu- t) for the hydrogenation of various ketones and imines to the respective alcohols and amines with H2 gas (1,11 atm) at room temperature. Acetophenone was hydrogenated to (S)-1-phenylethanol in low ee (up to 40%) when catalyzed by the enantiomerically pure complexes. These complexes are especially active in the hydrogenation of sterically congested and electronically deactivated ketones and imines and are selective for the hydrogenation of CO bonds over CC bonds. [source] Preparation and structures of a series of phosphorus-free Nickel(II) diamine complexes and their applications in hydrogenation of acetophenoneAPPLIED ORGANOMETALLIC CHEMISTRY, Issue 9 2010Zilu Chen Abstract To develop economical and phosphorus-free catalysts for hydrogenation of ketones, three new complexes, [Ni(1R,2R -dpen)2(H2O)Cl]2Cl2· 2Et2O (1), [Ni(1R,2R -dpen)(phen)(CH3OH)2]Cl2·2CH3OH (2) and [Ni(1,8-dan)2(DMF)Cl]2Cl2· 3H2O (3), and three reported compounds, [Ni(opda)(phen)Cl2]·CH3OH (4), [Ni(opda)2Cl2] (5) and [Ni(1,2-dach)2]Cl2 (6), were prepared and the structures of new compounds were determined by single crystal X-ray diffraction analysis, in which 1R,2R -dpen, phen, 1,8-dan, opda and 1,2-dach denote 1R,2R -1,2-diphenylethylenediamine, 1,10-phenanthroline, 1,8-diaminonaphthalene, o -phenylenediamine and 1,2-diaminocyclohexane, respectively. The catalytic effects for hydrogenation of acetophenone of these compounds were tested. This revealed very poor or no catalytic effects of these complexes in transfer hydrogenation of acetophenone using isopropanol or HCOOHNEt3 as hydrogen source. However, they presented much better catalytic effects in ionic hydrogenation of acetophenone using H2 gas as hydrogen source with a dependence of the catalytic effects on the base used in the hydrogenation reactions. The complexes represent a kind of green hydrogenation catalyst, although the conversion in the hydrogenation reactions is not as high as expected. Copyright © 2010 John Wiley & Sons, Ltd. [source] Hydrogen photoproduction by nutrient-deprived Chlamydomonas reinhardtii cells immobilized within thin alginate films under aerobic and anaerobic conditionsBIOTECHNOLOGY & BIOENGINEERING, Issue 1 2009Sergey N. Kosourov Abstract A new technique for immobilizing H2 -photoproducing green algae within a thin (<400 µm) alginate film has been developed. Alginate films with entrapped sulfur/phosphorus-deprived Chlamydomonas reinhardtii, strain cc124, cells demonstrate (a) higher cell density (up to 2,000 µg Chl mL,1 of matrix), (b) kinetics of H2 photoproduction similar to sulfur-deprived suspension cultures, (c) higher specific rates (up to 12.5 µmol,mg,1,Chl,h,1) of H2 evolution, (d) light conversion efficiencies to H2 of over 1% and (e) unexpectedly high resistance of the H2 -photoproducing system to inactivation by atmospheric O2. The algal cells, entrapped in alginate and then placed in vials containing 21% O2 in the headspace, evolved up to 67% of the H2 gas produced under anaerobic conditions. The results indicate that the lower susceptibility of the immobilized algal H2 -producing system to inactivation by O2 depends on two factors: (a) the presence of acetate in the medium, which supports higher rates of respiration and (b) the capability of the alginate polymer itself to effectively separate the entrapped cells from O2 in the liquid and headspace and restrict O2 diffusion into the matrix. The strategy presented for immobilizing algal cells within thin polymeric matrices shows the potential for scale-up and possible future applications. Biotechnol. Bioeng. 2008. Biotechnol. Bioeng. 2009;102: 50,58. © 2008 Wiley Periodicals, Inc. [source] Hydrogen Adsorption and Diffusion in p - tert -Butylcalix[4]arene: An Experimental and Molecular Simulation StudyCHEMISTRY - A EUROPEAN JOURNAL, Issue 38 2010Dr. Saman Alavi Abstract Experimental adsorption isotherms were measured and computer simulations were performed to determine the nature of the H2 gas uptake in the low-density p - tert -butylcalix[4]arene (tBC) phase. 1H,NMR peak intensity measurements for pressures up to 175,bar were used to determine the H2 adsorption isotherm. Weak surface adsorption (up to ,2,mass,% H2) and stronger adsorption (not exceeding 0.25,mass,% or one H2 per calixarene bowl) inside the calixarene phase were detected. The latter type of adsorbed H2 molecule has restricted motion and shows a reversible gas adsorption/desorption cycle. Pulsed field gradient (PFG) NMR pressurization/depressurization measurements were performed to study the diffusion of H2 in the calixarene phases. Direct adsorption isotherms by exposure of the calixarene phase to pressures of H2 gas to ,60,bar are also presented, and show a maximum H2 adsorption of 0.4,H2 per calixarene bowl. Adsorption isotherms of H2 in bulk tBC have been simulated using grand canonical Monte Carlo calculations in a rigid tBC framework, and yield adsorptions of ,1,H2 per calixarene bowl at saturation. Classical molecular dynamics simulations with a fully flexible calixarene molecular force field are used to determine the guest distribution and inclusion energy of the H2 in the solid with different loadings. [source] | ||||||||||