Rare-earth metal complexes stabilized by amino-phosphine ligand. Reaction with mesityl azide and catalysis of the cycloaddition of organic azides and aromatic alkynes

Stoichiometric reactions between mesityl azide (MesN(3), Mes = 2,4,6-C6H2Me3) and amino-phosphine ligated rare-earth metal alkyl, LLn(CH2SiMe3) (2)(THF) (L = (2,6-C6H3Me2)NCH2C6H4P(C6H5)(2); Ln = Lu (1a), Sc (1b)), amide, LLu(NH(2,6-(C6H3Pr2)-Pr-i))(2)(THF) (2) and acetylide at room temperature gave the amino-phosphazide ligated rare-earth metal bis(triazenyl) complexes, [L(MesN(3))]Ln[(MesN(3))-(CH2SiMe3)](2) (Ln = Lu (3a); Sc (3b)), bis(amido) complex [L(MesN3)] Lu[NH(2,6-C6H3 Pr-i(2))](2) (4), and bis(alkynyl) complex (5) (L(MesN(3))Lu (C CPh)(2))(2), respectively. The triazenyl group in 3 coordinates to the metal ion in a rare eta(2)-mode via N-beta and N-gamma atoms, generating a triangular metallocycle. The amino-phosphazide ligand, L(MesN(3)), in 3, 4 and 5 chelates to the metal ion in a eta(3)-mode via N-alpha and N-gamma atoms. In the presence of excess phenylacetylene, complex 3a isomerized to 3', where the triazenyl group coordinates to the metal ion in a eta(3) mode via Na and Ng atoms.

Electrochemical catalysis and thermal stability characterization of laccase-carbon nanotubes-ionic liquid nanocomposite modified graphite electrode

The hydrophobic carbon nanotubes-ionic liquid (CNTs-IL) get forms a stable modified film on hydrophobic graphite electrode surface. Laccase immobilized on the CNTs-IL gel film modified electrode shows good thermal stability and enhanced electrochemical catalytic ability. The optimal bioactivity occurs with increasing temperature and this optimum is 20 degrees C higher in comparison to free laccase. The improvement of laccase thermal stability may be due to the microenvironment of hydrophobic CNTs-IL gel on graphite electrode surface. On the other hand, the sensitive detection of oxygen has been achieved due to the feasibility of oxygen reduction by both of laccase and nanocomposite of CNTs-IL gel. Furthermore, the laccase hybrid nanocomposite also shows the fast electrochemical response and high sensitivity to the inhibitors of halide ions with the approximate IC50 of 0.01, 4.2 and 87.5 mM for the fluoride, chloride and bromide ions, respectively. It implies the feasibility of laccase modified electrode as an inhibition biosensor to detect the modulators of laccase.

Achiral lanthanide alkyl complexes bearing N,O multidentate ligands. Synthesis and catalysis of highly heteroselective ring-opening polymerization of rac-lactide

Alkane elimination reactions of amino-amino-bis(phenols) H2L1-4, Salan H2L5, and methoxy-beta-diimines HL6,7 with lanthanide tris(alkyl) s, Ln(CH2SiMe3)(3)(THF)(2) (Ln = Y, Lu), respectively, afforded a series of lanthanide alkyl complexes 1-8 with the release of tetramethylsilane. Complexes 1-6 are THF-solvated mono( alkyl) s stabilized by O, N, N, O-tetradentate ligands. Complexes 1-3 and 5 adopt twisted octahedral geometry, whereas 4 contains a tetragonal bipyramidal core. Bearing a monoanionic moiety L-6 (L-7), complex 7 ( 8) is a THF-free bis(alkyl). In complex 7, the O, N, N-tridentate ligand combined with two alkyl species forms a tetrahedral coordination core. Complexes 1, 2, and 3 displayed modest activity but high stereoselectivity for the polymerization of rac-lactide to give heterotactic polylactide with the racemic enchainment of monomer units P-r ranging from 0.95 to 0.99, the highest value reached to date. Complex 5 exhibited almost the same level of activity albeit with relatively low selectivity. In contrast, dramatic decreases in activity and stereoselectivity were found for complex 4. The Salan yttrium alkyl complex 6 was active but nonselective. Bis(alkyl) complexes 7 and 8 were more active than 1-3 toward polymerization of rac-LA, however, to afford atactic polylactides due to di-active sites. The ligand framework, especially the "bridge" between the two nitrogen atoms, played a significant role in governing the selectivity of the corresponding complexes via changing the geometry of the metal center.

Rare earth metal alkyl complexes bearing N,O,P multidentate ligands: Synthesis, characterization and catalysis on the ring-opening polymerization of L-lactide

Alkane elimination reactions of rare earth metal tris(alkyl)s, Ln(CH2SiMe3)3(THF)2 (Ln = Y, Lu) with the multidentate ligands HL1-4, afforded a series of new rare earth metal complexes. Yttrium, complex I supported by flexible amino-intino phenoxide ligand HL1 was isolated as homoleptic product. In the reaction of rigid phosphino-imino phenoxide ligand HL 2 with equintolar Ln(CH2SiMe3)3(THF)2, HL 2 was deprotonated by the metal alkyl and its imino C=N group was reduced to C-N by intramolecular alkylation, generating THF-solvated mono-alkyl complexes (2a: Ln = Y; 2b: Ln = Lu). The di-ligand chelated yttriurn complex 3 without alkyl moiety was isolated when the molar ratio of HL 2 to Y(CH,SiMe3)3(THF)2 increased to 2: 1. Reaction of steric phosphino beta-ketoiminato ligand HL 3 with equimolar Ln(CH2SiMe3)3(THF)2 afforded di-ligated mono-alkyl complexes (4a: Ln = Y; 4b: Ln = Lu) without occurrence of intramolecular alkylation or formation of homoleptic product. Treatment of tetradentate methoxy-amino phenol HL 4 with Y(CH2SiMe3)3(THF)2 afforded a monomeric yttrium bis-alkyl complex of THF-free. The resultant complexes were characterized by IR, NMR spectrum and X-ray diffraction analyses.All alkyl complexes exhibited high activity toward the ring-opening polymerization Of L-lactide to give isotactic polylactide with controllable molecular weight and narrow to moderate polydispersity.

Mixed ligands supported yttrium alkyl complexes: Synthesis, characterization and catalysis toward lactide polymerization

Treatment of yttrium tris(alkyl)s, Y(CH2SiMe3)(3)(THF)(2), by equimolar H(C5Me4)SiMe3(HCp') and indene (Ind-H) afforded (eta(5)-Cp')Y(CH2SiMe3)(2)(THF) (1) and (eta(5)-Ind)Y(CH2SiMe3)(2)(THF) (2) via alkane elimination, respectively. Complex 1 reacted with methoxyamino phenols, 4,6-(CH3)(2)-2-[(MeOCH2CH2)(2)-NCH2]-C6H2-OH (HL1) and 4,6-(CMe3)(2)-2-[(MeOCH2CH2)(2)-NCH2]-C6H2OH (HL2) gave mixed ligands supported alkyl complexes [(eta(5)-Cp')(L)]Y(CH2SiMe3) (3: L = L-1; 4: L = L-2). Whilst, complex 2 was treated with HL2 to yield [(eta(5)-Ind)(L-2)]Y(CH2SiMe3) (5). The molecular structures of 3 and 5 were confirmed by X-ray diffraction to be mono(alkyl)s of THF-free, adopting pyramidal and tetragonal-bipyramidal geometry, respectively. Complexes 3 and 5 were high active initiators for the ring-opening polymerization Of L-lactide to give isotactic polylactide with high molecular weight and narrow to moderate polydispersity.

Electropolymerization and catalysis of well-dispersed polyaniline/carbon nanotube/gold composite

Polyaniline/multi-walled carbon nanotube/gold (PANI/MWNT/Au) composite film was synthesized via a two-step electrochemical process. First the mixture of aniline and MWNT was heated at refluxing and was electropolymerized. Then, the An nanoparticles were dispersed into the film of PANI/MWNT by electrochemical reduction of HAuCl4. The morphology of sample was analyzed by scanning electron microscopy (SEM). Raman measurement indicates a well electrochemical deposition of PANI on MWNT, and XPS result confirms the formation of Au-0 nanoparticles. Further, cyclic voltammograms show that the film exhibits a good electrochemical activity and electrocatalysis towards ascorbic acid. Based on these investigations, a formation mechanism of the PANI/MWNT composite film was proposed.

Influences of catalysis and dispersion of organically modified montmorillonite on flame retardancy of polypropylene nanocomposites

The degradation and flame retardancy of polypropylene/organically modified montmorillonite (PP/OMMT) nanocomposite were studied by means of gas chromatography-mass spectrometry and cone calorimeter. The catalysis of hydrogen proton containing montmorillonite (H-MMT) derived from thermal decomposition of (alkyl) ammonium in the OMMT on degradation of PP strongly influence carbonization behavior of PP and then flame retardancy. Bronsted acid sites on the H-MMT could catalyze degradation reaction of PP via cationic mechanism, which leads to the formation of char during combustion of PP via hydride transfer reaction. A continuous carbonaceous MMT-rich char on the surface of the burned residues, which work as a protective barrier to heat and mass transfer, results from the homogeneous dispersion of OMMT in the PP matrix and appropriate char produced.

Microwave-assisted synthesis of high-molecular-weight poly(ether imide)s by phase-transfer catalysis

A facile and rapid polycondensation reaction of disodium bisphenol A with bis(chlorophthalimide)s was preformed with a domestic microwave oven in o-dichlorobenzene by phase-transfer catalysis. The polymerization reactions, in comparison with conventional heating polycondensation, proceeded rapidly and were completed within 25 min. The polymerizations gave the corresponding poly(ether imide)s with inherent viscosities of 0.55-0.92 dL g(-1). The effects of various factors on the polymerization, such as the amount of the catalyst, the reaction time, and the microwave power were studied. The properties of the polymers were briefly characterized.

Fabrication of core-shell Au-Pt nanoparticle film and its potential application as catalysis and SERS substrate

In this paper we report the rational design and fabrication of high-quality core-shell Au-Pt nanoparticle film. Such film shows highly efficient catalytic properties and excellent surface-enhanced Raman scattering (SERS) ability.

Cyclic voltammetry for predicting oxidation process in heterogeneous catalysis

Catalytic reactions with different oxidation process were investigated and correlated to the electrochemical properties of the catalysts. The activity of suprafacial reaction is closely related to the area of redox peak, while that of the intrafacial one is to the match of redox potentials. Accordingly, it is supposed that cyclic voltammetry (CV) measurement could be a means for predicting the oxidation process in heterogeneous catalysis.

Fabrication of a metalloporphyrin - Polyoxometalate hybrid film by a layer-by-layer method and its catalysis for hydrogen evolution and dioxygen reduction

Tetrakis (N-methylpyridyl) porphyrinato] cobalt (CoTMPyP) and 1:12 silicotungstic acid (SiW12) were alternately deposited on a 4-aminobenzoic acid (4-ABA)-modified glassy carbon electrode through a layer-by-layer method. The resulting organic-inorganic hybrid films were characterized by cyclic voltammetry (CV) and UV/vis absorption spectroscopy. We proved that the prepared multilayer films are uniform and stable. SiW12-containing multilayer films (SiW12 as the outermost layer) exhibit remarkable electrocatalytic activity for the hydrogen evolution reaction (HER). The kinetic constants for HER were comparatively investigated at different layers Of SiW12/CoTMPyP multilayer film-modified electrodes by hydrogen evolution voltammetry. In addition, rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) voltammetric methods confirm that SiW12/CoTMPyP (CoTMPyP as the outermost layer) multilayer films catalyze almost a two-electron reduction of O-2 to H2O2 in pH 1-6 buffer solutions. Furthermore, P2W18/CoTMPyP films were also assembled, and their catalytic activity for HER is very different from that Of SiW12/CoTMPyP multilayer films.

Simple preparation method of Pd nanoparticles on an Au electrode and its catalysis for dioxygen reduction

A simple method for the fabrication of Pd nanoparticles is described. The three-dimensional Pd nanoparticle films are directly formed on a gold electrode surface by simple electrodeposition at -200 mV from a solution of 1 M H2SO4+0.01 mM K2PdCl4. X-Ray photoelectron spectroscopy verifies the constant composition of the Pd nanoparticle films. Atomic force microscopy proves that the as-prepared Pd nanoparticles are uniformly distributed with an average particle diameter of 45-60 nm. It is confirmed that the morphology of the Pd nanoparticle films are correlated with the electrodeposition time and the state of the Au substrate. The resulting Pd-nanoparticle-film-modified electrode possesses high catalytic activity for the reduction of dissolved oxygen in 0.1 M KCl solution. Freshly prepared Pd nanoparticles can catalyze the reduction of O-2 by a 4-electron process at -200 mV in 0.1 M KCl, but this system is not very stable. The cathodic peaks corresponding to the reduction of O-2 gradually decrease with potential cycling and at last reach a steady state. Then two well-defined reduction peaks are observed at -390 and -600 mV vs. Ag/AgCl/KCl (sat.). Those two peaks correspond to a 2-step process for the 4-electron reduction pathway of O-2 in this neutral medium.