Metal‐Catalyzed “On‐Demand” Production of Carbonyl Sulfide from Carbon Monoxide and Elemental Sulfur

The group 6 molybdenum(II) cyclopentadienyl amidinate (CPAM) bis(carbonyl) complex [Cp*Mo{N(iPr)C(Ph)N(iPr)}(CO)₂] (Cp*=η⁵‐C₅Me₅) serves as a precatalyst for the high‐yielding photocatalytic production of COS from CO and S₈ under near‐ambient conditions (e.g., 10 psi, 25 °C). Further documented is the isolation and structural characterization of several key transition‐metal intermediates which collectively support a novel molybdenum(IV)‐based catalytic cycle as being operative. Finally, in the presence of an excess amount of a primary amine, it is demonstrated that this catalytic system can be successfully used for the “on‐demand” generation and utilization of COS as a chemical reagent for the synthesis of ureas.     

Synthesis,Crystal Structure and Catalytic Properties of a 2D Cobalt(Ⅱ) Coordination Polymer Based on Mixed Ligands

A new Co(II) metal-organic coordination polymer based on flexible bis(imidazole) and aromatic dicarboxylate co-ligands, namely [Co(bix)(nph)]n(H2nph = 3-nitrophthalic acid, bix = 1,4-bis(imidazole-1-ylmethyl)benzene), has been hydrothermally synthesized and characterized by elemental analyses, TG, IR spectroscopy and single-crystal X-ray diffraction. It crystallizes in the triclinic space group P1 with a = 9.3767(14), b = 10.1451(15), c = 12.1488(17), α = 102.6450(10), β = 108.856(2), γ = 98.807(2)°, V = 1035.3(3)3, Z = 2, C22H17 Co N5O6, Mr = 506.34, Dc = 1.624 g/cm3, μ = 0.882 mm-1 and F(000) = 518. In the complex, the nph2- ligands connect neighbouring cobalt atoms to form binuclear [Co(nph)]2 subunits, which are linked by pairs of bix ligands to form a 2D honeycomb-like(6,3) network. In addition, the compound is further extended into a 3D supramolecular architecture by π···π stacking interactions. Moreover, the luminescence and catalytic properties of the complex are investigated.     

Synthesis and characterization of nano Ag end capped L-cysteine bridged diblock copolymer

The target of the present investigation is synthesis and characterization of an amphiphilic diblock copolymer with antibacterial property. Ring opening polymerization (ROP) of ε-caprolactone (CL) and tetrahydrofuran (THF) was carried out under inert atmosphere by using L-cysteine as a bridging agent in the presence of stannous octoate (SO) as a catalyst. The nano silver end capped diblock copolymer was synthesized by in situ method. Thus obtained nano silver end capped L-cysteine bridged diblock copolymer was characterized by various analytical methods like Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, circular dichroism (CD), fluorescence spectroscopy, gel permeation chromatography (GPC), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), field emission scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM) and zeta potential. The antimicrobial property of the nano silver end capped diblock copolymer against e-coli was tested.     

Pulsed Plasma Assisted Growth of Vertically Aligned Carbon Nanotubes at Low Temperature on Mo Substrate

Plasma Chemistry and Plasma Processing - Aligned carbon nanotubes (CNTs)/carbon nanofibers (CNFs) are synthesized at temperatures of 350, 400 and 450 °C using pulsed plasma enhanced...     

Direct Photoredox‐Catalyzed Reductive Difluoromethylation of Electron‐Deficient Alkenes

Photoredox‐catalyzed reductive difluoromethylation of electron‐deficient alkenes was achieved in one step under tin‐free, mild and neutral conditions. This protocol affords a facile method to introduce RCF₂ (R=H, Ph, Me, and CH₂N₃) groups at sites β to electron‐withdrawing groups. It was found that TTMS (tris(trimethylsilyl)silane) served nicely as both the H‐atom donor and the electron donor in the catalytic cycle. Experimental and DFT computational results provided evidence that RCF₂ (R=H, Ph, Me) radicals are nucleophilic in nature.     

Cooperative Bond Activation and Catalytic Reduction of Carbon Dioxide at a Group 13 Metal Center

A single‐component ambiphilic system capable of the cooperative activation of protic, hydridic and apolar H? X bonds across a Group 13 metal/activated β‐diketiminato (Nacnac) ligand framework is reported. The hydride complex derived from the activation of H₂ is shown to be a competent catalyst for the highly selective reduction of CO₂ to a methanol derivative. To our knowledge, this process represents the first example of a reduction process of this type catalyzed by a molecular gallium complex.     

Increased Water Reduction Efficiency of Polyelectrolyte‐Bound Trimetallic [Ru,Rh,Ru] Photocatalysts in Air‐Saturated Aqueous Solutions

The groundbreaking use of polyelectrolytes to increase the efficiency of supramolecular photocatalysts in solar H₂ production schemes under aqueous aerobic conditions is reported. Supramolecular photocatalysts of the architecture [{(TL)₂Ru(BL)}₂RhX₂]⁵⁺ (BL=bridging ligand, TL=terminal ligand, X=halide) demonstrate high efficiencies in deoxygenated organic solvents but do not function in air‐saturated aqueous solution because of the quenching of the metal‐to‐ligand charge‐transfer (MLCT) excited state under these conditions. The new photocatalytic system incorporates poly(4‐styrenesulfonate) (PSS) into aqueous solutions containing [{(bpy)₂Ru(dpp)}₂RhCl₂]⁵⁺ (bpy=2,2′‐bipyridine, dpp=2,3‐bis(2‐pyridyl)pyrazine). PSS has a profound impact on the photocatalyst efficiency, increasing H₂ production over three times that of deoxygenated aqueous solutions alone. H₂ photocatalysis proceeds even under aerobic conditions for PSS‐containing solutions, an exciting consequence for solar hydrogen‐production research.