Transfer hydrogenation of aryl ketones with homogeneous ruthenium catalysts containing diazafluorene ligands

Novel cationic ruthenium(II) complexes bearing a 4,5‐diazafluorene unit and p‐cymene as ligands have been synthesised. The complexes were characterised based on elemental analysis and Fourier transform infrared and nuclear magnetic resonance spectroscopies. The synthesised Ru(II) complexes were employed as pre‐catalysts for the transfer hydrogenation of aromatic ketones using 2‐propanol as both hydrogen source and solvent in the presence of NaOH. All complexes showed high catalytic activity as catalysts in the reduction of substituted acetophenones to corresponding secondary alcohols. The products of catalysis were obtained with conversion rates of between 80 and 99%. Among the seven new complexes investigated, the most efficient catalyst showed turnover frequencies in the range 255–291 h^?1 corresponding to 85 to 97% conversion, respectively. Copyright © 2016 John Wiley & Sons, Ltd.     

Organozinc Pivalate Reagents: Segregation,Solubility, Stabilization,and Structural Insights

The pivalates RZnOPiv⋅Mg(OPiv)X⋅n LiCl (OPiv=pivalate; R=aryl; X=Cl, Br, I) stand out amongst salt‐supported organometallic reagents, because apart from their effectiveness in Negishi cross‐coupling reactions, they show more resistance to attack by moist air than conventional organometallic compounds. Herein a combination of synthesis, coupling applications, X‐ray crystallographic studies, NMR (including DOSY) studies, and ESI mass spectrometric studies provide details of these pivalate reagents in their own right. A p‐tolyl case system shows that in [D₈]THF solution these reagents exist as separated Me(p‐C₆H₄)ZnCl and Mg(OPiv)₂ species. Air exposure tests and X‐ray crystallographic studies indicate that Mg(OPiv)₂ enhances the air stability of aryl zinc species by sequestering H₂O contaminants. Coupling reactions of Me(p‐C₆H₄)ZnX (where X=different salts) with 4‐bromoanisole highlight the importance of the presence of Mg(OPiv)₂. Insight into the role of LiCl in these multicomponent mixtures is provided by the molecular structure of [(THF)₂Li₂(Cl)₂(OPiv)₂Zn].     

A transparent solid-state ion gel for supercapacitor device applications

Journal of Solid State Electrochemistry - A feasibility study of the synthesis of gel polymer electrolytes based in methyl methacrylate (MMA) and 1-vinyl-2-pyrrolidone (VP) using [HEMIm][BF4] as...     

Comparison of different electrode arrangements for gas decomposition efficiency using experimental method

The environmental pollution is a central issue in the present industrial societies. Within that the air pollution and the removal of hazardous components of flue and exhaust gases are very much important.In this paper the target is to decrease of the NO_x emission by means of a technology similar to that is used in the electrostatic precipitators. In most of the papers dealing with this technique cylindrical precipitator is used as a discharge chemical reactor, and fast rising electric discharges are applied for energizing the reactor. In the industry the over helming majority of the electrostatic precipitators are plate type one.In the cylindrical precipitator the discharge electrode is parallel with the gas flow, and the corona discharge filament is perpendicular to both of them. In the case of plate type industrial electrostatic precipitator the discharge electrodes are positioned vertically, and the flow of the flue gas is horizontal. Consequently, the discharge filaments are mainly perpendicular to both the flow and the discharge electrode.In cylindrical precipitator the decomposition of NO_x is done in one filament very soon, but there is no chance to modify the byproducts with a new pulse, because the energization is the same for the whole length of the discharge electrode.In the present paper a cylindrical precipitator, a plate type precipitator with horizontal electrode, and a plate type precipitator with vertical electrode were tested. The total length of the discharge electrodes of all of the precipitators was the same.The results of the NO_x decomposition were experimentally determined, and the differences between the precipitators were investigated. The cylindrical and the plate type precipitators with vertical electrodes had shown basically similar decomposition rate, while the plate type one with horizontal discharge electrode had proven inferior to the others.     

Comment on “Density functional theory study of 1,2‐dioxetanone decomposition in condensed phase”

In the preceding paper results are presented, which are in serious conflict with state‐of‐the‐art ab initio method. Based on these new results the authors propose a new explanation of the reason for the preferential production of a phosphorescent state. Here we show that these controversial results are flawed, since the model use exclude biradical electron structures. © 2012 Wiley Periodicals, Inc.     

A Kochen-Specker inequality from a SIC

Yu and Oh (eprint) [1] have given a state-independent proof of the Kochen-Specker theorem in three dimensions using only 13 rays. The proof consists of showing that a non-contextual hidden variable theory necessarily leads to an inequality that is violated by quantum mechanics. We give a similar proof making use of 21 rays that constitute a SIC (symmetric informationally-complete positive operator-valued measure) and a complete set of MUB (mutually unbiased bases). A theory-independent inequality is also presented using the same 21 rays, as required for experimental tests of contextuality.