Highly Proton-Conductive Zinc Metal-Organic Framework Based On Nickel(II) Porphyrinylphosphonate

The design of new solid-state proton-conducting materials is a great challenge for chemistry and materials science. Herein, a new anionic porphyrinylphosphonate-based MOF ( IPCE-1Ni ), which involves dimethylammonium (DMA) cations for charge compensation, is reported. As a result of its unique structure, IPCE-1Ni exhibits one of the highest value of the proton conductivity among reported proton-conducting MOF materials based on porphyrins (1.55×10⁻³ S cm⁻¹ at 75 °C and 80 % relative humidity).     

The Aza‐Morita–Baylis–Hillman Reaction: A Mechanistic and Kinetic Study

The aza‐Morita‐Baylis–Hillman (aza‐MBH) reaction has been studied in a variety of solvents, a selection of imine substrates and with various combinations of PPh₃ and para‐nitrophenol as the catalyst system. The measured kinetic data indicates that the effects of solvent and protic co‐catalyst are strongly interdependent. These results are most easily reconciled with a mechanistic model involving the reversible protonation of zwitterionic intermediates in the catalytic cycle, which is also supported by ³¹P NMR spectroscopy and quantum chemical studies.     

H-, C-NMR and ethylene polymerization studies of zirconocene/MAO catalysts: effect of the ligand structure on the formation of active intermediates and polymerization kinetics

Using ¹H- and ¹³C-NMR spectroscopies, cationic intermediates formed by activation of L₂ZrCl₂ with methylaluminoxane (MAO) in toluene were monitored at Al/Zr ratios from 50 to 1000 (L₂ are various cyclopentadienyl (Cp), indenyl (Ind) and fluorenyl (Flu) ligands). The following catalysts were studied: (Cp-R)₂ZrCl₂ (R=Me, 1,2-Me₂, 1,2,3-Me₃, 1,2,4-Me₃, Me₄, Me₅, n-Bu, t-Bu), rac-ethanediyl(Ind)₂ZrCl₂, rac-Me₂Si(Ind)₂ZrCl₂, rac-Me₂Si(1-Ind-2-Me)₂ZrCl₂, rac-ethanediyl(1-Ind-4,5,6,7-H₄)₂ZrCl₂, (Ind-2-Me)₂ZrCl₂, Me₂C(Cp)(Flu)ZrCl₂, Me₂C(Cp-3-Me)(Flu)ZrCl₂ and Me₂Si(Flu)₂ZrCl₂. Correlations between spectroscopic and ethene polymerization data for catalysts (Cp-R)₂ZrCl₂/MAO (R=H, Me, 1,2-Me₂, 1,2,3-Me₃, 1,2,4-Me₃, Me₄, Me₅, n-Bu, t-Bu) and rac-Me₂Si(Ind)₂ZrCl₂ were established. The catalysts (Cp-R)₂ZrCl₂/AlMe₃/CPh₃⁺B(C₆F₅)₄⁻ (R=Me, 1,2-Me₂, 1,2,3-Me₃, 1,2,4-Me₃, Me₄, n-Bu, t-Bu) were also studied for comparison of spectroscopic and polymerization data with MAO-based systems. Complexes of type (Cp-R)₂ZrMe⁺←Me⁻-Al≡MAO (IV) with different [Me-MAO]⁻ counteranions have been identified in the (Cp-R)₂ZrCl₂/MAO (R=n-Bu, t-Bu) systems at low Al/Zr ratios (50-200). At Al/Zr ratios of 500-1000, the complex [L₂Zr(μ-Me)₂AlMe₂]⁺[Me-MAO]⁻ (III) dominates in all MAO-based reaction systems studied. Ethene polymerization activity strongly depends on the Al/Zr ratio (Al/Zr=200-1000) for the systems (Cp-R)₂ZrCl₂/MAO (R=H, Me, n-Bu, t-Bu), while it is virtually constant in the same range of Al/Zr ratios for the catalytic systems (Cp-R)₂ZrCl₂/MAO (R=1,2-Me₂, 1,2,3-Me₃, 1,2,4-Me₃, Me₄) and rac-Me₂Si(Ind)₂ZrCl₂/MAO. The data obtained are interpreted on assumption that complex III is the main precursor of the active centers of polymerization in MAO-based systems.     

Correction to: The effect of small silver inclusions on the palladium activity in formicacid oxidation reaction and corrosion stability

A PdAg deposit containing ~ 25 at.% Ag is obtained by the electrochemical codeposition from an aqueous solution of Pd and Ag sulfates (Au support, 0.5 M H₂SO₄). The deposit is characterized by means of various physical, physicochemical, and electrochemical methods. The PdAg deposit demonstrates the ~ 2 times higher specific activity (per the electrochemically active surface area (EASA) of Pd) in the formic acid oxidation reaction (FAOR) as compared with the individual Pd deposit prepared under the same conditions. The effect of silver additions on the palladium activity depends on many factors. The corrosion stability of PdAg is studied in 0.5 M H₂SO₄ solution based on the overall cyclic voltammograms (CVAs) and also on anodic and cathodic half-cycles in the region E = 0.3 − 1.25 V (vs. reversible hydrogen electrode (RHE)). The electrochemical estimates are compared with the results of direct analytical determination of dissolution products in solution after anodic polarization of deposits. The total amounts of Pd dissolved substantially increase with incorporation of Ag, which is associated, first of all, with the considerable increase in the EASA; at the same time, the specific dissolution of Pd also substantially increases. The possible factors determining the active dissolution of PdAg deposits are discussed; in particular, the specific mechanism of their dissolution via silver adatoms is proposed.

     

Synthesis,Properties and Reactivity Studies of a Hetero-dicopper Complex Consisting of a Porphyrin and a Bispyridylamine Moiety Connected by a Xanthene Backbone

Synthesis, characterization and reactivity studies of a hetero-dicopper complex, particularly towards oxygen reduction are presented. A bischlorido copper(II) trishistidine-type coordination unit is positioned directly above a copper porphyrin unit. The close distance between the two coordination fragments is secured by a rigid xanthene backbone. Surprisingly, the dinuclear complex is not active towards oxygen reduction unlike the earlier published mononuclear analogues with a bispyridylamine copper center. However, the compound architecture of this multinuclear metal complex is interesting and can play an important role in the development of new catalysts for ORR.     

Exposing the Oxygen-Centered Radical Character of the Tetraoxido Ruthenium(VIII) Cation [RuO4]+

The tetraoxido ruthenium(VIII) radical cation, [RuO₄]⁺, should be a strong oxidizing agent, but has been difficult to produce and investigate so far. In our X-ray absorption spectroscopy study, in combination with quantum-chemical calculations, we show that [RuO₄]⁺, produced via oxidation of ruthenium cations by ozone in the gas phase, forms the oxygen-centered radical ground state. The oxygen-centered radical character of [RuO₄]⁺ is identified by the chemical shift at the ruthenium M₃ edge, indicative of ruthenium(VIII), and by the presence of a characteristic low-energy transition at the oxygen K edge, involving an oxygen-centered singly-occupied molecular orbital, which is suppressed when the oxygen-centered radical is quenched by hydrogenation of [RuO₄]⁺ to the closed-shell [RuO₄H]⁺ ion. Hydrogen-atom abstraction from methane is calculated to be only slightly less exothermic for [RuO₄]⁺ than for [OsO₄]⁺.     

3-Cyanoazolo[5,1-c][1,2,4]triazines: synthesis and antiviral activity

Chemistry of Heterocyclic Compounds - A series of azolo[5,1-c][1,2,4]triazines containing a cyano group were prepared as analogs of the drug Triazavirin (riamilovir). Sodium...     

Synthesis and structure of anhydroindanone‐1 disulfide

An unexpectedly high yield of anhydroindanone‐1 disulfide (1) was obtained by reaction of Lawesson's reagent with indanone‐1. The molecular structure of 1 was established by X‐ray diffraction. A possible mechanism of the reaction is discussed. © 1999 John Wiley & Sons, Inc. Heteroatom Chem 10: 369–371, 1999