Rare-Earth Metal Bis(alkyl)s Supported by a Quinolinyl Anilido-Imine Ligand: Synthesis and Catalysis on Living Polymerization of epsilon-Caprolactone

The tridentate ligand N-(2-((2,6-diisopropylphenylimino)methyl)phenyl)quinolin-8-amine (HL) was prepared. Treatment of HL with 1 equiv of Ln(CH2SiMe3)(3)(THF)(2) afforded the corresponding rare-earth metal bis(alkyl) complexes LLn(CH2SiMe3)(2)(THF)(n) (Ln = Sc, n = 0 (1); Y, n = 1 (2); Lu, n = 0 (3)) in high yields. Variable-temperature H-1 NMR spectral analysis showed that these complexes were fluxional at room temperature. Complexes 1 and 3 were THF-free, where the metal center adopted a square-pyramidal geometry, while in 2 the metal center generated a distorted octahedral geometry owing to the coordination of a THF molecule.

Highly cis-1,4 selective polymerization of dienes with homogeneous Ziegler-Natta catalysts based on NCN-pincer rare earth metal dichioride precursors

The first aryldiimine NCN-pincer ligated rare earth metal dichlorides (2,6-(2,6-C6H3R2N=CH)(2)C6H3)LnCl(2)(THF)(2) (Ln = Y, R = Me (1), Et (2), Pr (3); R = Et, Ln = La (4), Nd (5), Gd (6), Sm (7), Eu (8), Tb (9), Dy (10), Ho (11), Yb (12), Lu (13)) were successfully synthesized via transmetalation between 2,6-(2,6-C2H3-R2N=CH)(2)-C6H3Li and LnCl(3)(THF)(1 similar to 3.5). These complexes are isostructural monomers with two coordinating THF molecules, where the pincer ligand coordinates to the central metal ion in a kappa C:kappa N: kappa N' tridentate mode, adopting a meridional geometry.

Constructing porous frameworks from one-dimensional cobalt-oxygen clusters and pyridinedicarboxylate ligands adopting two rare coordination modes

A porous material with cobalt-oxygen cluster framework has been synthesized hydrothermally, which possesses large and rigid channels and manifests strong antiferromagnetic interactions, and the pyridinedicarboxylate ligand exhibits two types of rare coordination modes.

Carbon-supported Pd nanocatalyst modified by non-metal phosphorus for the oxygen reduction reaction

A carbon-supported palladium catalyst modified by non-metal phosphorus(PdP/C) has been developed as an oxygen reduction catalyst for direct methanol fuel cells.The PdP/C catalyst was prepared by the sodium hypophosphite reduction method. The as-prepared Pd nanoparticles have a narrow size distribution with an average diameter of 2 nm. Energy dispersive X-ray analysis (EDX), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD) results indicate that P enters into the crystal lattice of Pd and forms an alloy.

A three-dimensional metal-organic framework based on a triazine derivative: syntheses, structure analysis, and sorption studies

A novel metal-organic framework [Cu-3(m-TATB)(2)Py(CH3OH)(2)] (1) constructed of a triazine-based trigonal-planar ligand, 3,3',3 ''-s-triazine-2,4,6- triyltribenzoate (m-H(3)TATB), has been synthesized and structurally characterized. Compound 1 features three-dimensional (3D) channels and cavities together, and exhibits high carbon dioxide sorption at normal pressure.

Living polymerization of 1,3-butadiene by a Ziegler-Natta type catalyst composed of iron(III) 2-ethylhexanoate, triisobutylaluminum and diethyl phosphite

Living characteristics of facilely prepared Ziegler-Natta type catalyst system consisting of iron(III) 2-ethylhexanoate, triisobutylaluminum and diethyl phosphite have been found in the polymerization of 1,3-butadiene in hexane at 40 degrees C. The characteristics have been well demonstrated by: a first-order kinetics with respect to monomer conversion, a narrow molecular weight distribution (M-w/M-n = 1.48-1.52) of polybutadiene in the entire range of polymerization conversion and a good linearity between M-n and the yield of polymer. Feasible post-polymerization of 1,3-butadiene and block co-polymerization of 1,3-butadiene and isoprene further support the living natures of the catalyst bestowed with.

Entangled metal-organic frameworks modulated by N-donor ligands of different conformations

Based on the aromatic dicarboxylic acid and N-donor ligands with different conformations, four Zn(II) metal-organic frameworks, namely [Zn(mfda)(L-1)](1), [Zn-2(mfda)(2)(L-2)]center dot DMF center dot H2O (2), [Zn-2(mfda)(2)(L-3)(H2O)]center dot DMF (3) and [Zn-2(mfda)(2)(L-4)] (4) have been synthesized (mfda = 9,9-dimethylfluorene-2,7-dicarboxylate anion, L-1 = 1,10-phenanthroline, L-2 = 4,4 '-bipyridine, L-3 = 2,5-bis(4-pyridyl)-1,3,4-ocadiazole and L-4 = 1,4-bis(imidazol-1-ylmethyl)benzene). Single-crystal X-ray diffraction has revealed that all compounds exhibit entangled structures. Compound 1 is composed of 1D zigzag chains that are entangled through the pi-pi stacking interactions to generate a three-fold interpenetrating diamond-like networks.

Magnesium-Based 3D Metal-Organic Framework Exhibiting Hydrogen-Sorption Hysteresis

A new magnesium metal-organic framework (MOF) based on an asymmetrical ligand, biphenyl-3,4',5-tricarboxylate (H3PT) has been synthesized and structurally characterized. MOF Mg-3(BPT)(2)(H2O)(4) (1) consists of 10 hexagonal nanotube-like channels and exhibits pronounced hydrogen-sorption hysteresis at medium pressure.

Hydrothermal Synthesis, Structures, and Luminescent Properties of Seven d(10) Metal-Organic Frameworks Based on 9,9-Dipropylfluorene-2,7-Dicarboxylic Acid (H(2)DFDA)

A series of Zn(II) and Cd(II) metal-organic frameworks, namely, [Zn(DFDA)] (1), [Cd(DFDA)(C2H5OH)] (2), [Zn-2(DFDA)(2)(L-1)(2)](2) center dot 3H(2)O (3), [Cd-2(DFDA)(2)(L-1)(2)] (4), [Zn(DFDA)(L-2)] (5), [Cd(DFDA)(L-2)(DMF)] (6), and [Zn(DFDA)(L-3)] (7) (where DFDA = 9,9-dipropylfluorene-2,7-dicarboxylate anion, L-1 = 1,4-bis(imidazol-1-ylmethyl)benzene, L-2 = 1,1'-(1,4-butanediyl) bis(imidazole), L-3 = 2,2'-bipyridine) have been synthesized under hydrothermal conditions and structurally characterized. Compound 1 exhibits a three-dimensional (3D framework containing one-dimensional (1D) Zn(II)-O clusters, with (4(8).6(7)) topology. Compound 2 contains hydrophobic channels built from infinite 1D Cd(II)-O clusters, with (4(8).5(4).6(3)) topology.

Interweaving of single-helical and equal double-helical chains with the same helical axis in a 3D metal-organic framework

A novel metal-organic framework with unprecedented interweaving of coaxial single-helical and equal double-helical chains of opposite chirality, which features a super-connective helix simultaneously tangling with eight helices, was reported.

3D metal-organic frameworks incorporating water-soluble tetra-p-sulfonatocalix[4]arene

Water-soluble tetra-p-sulfonatocalix[4]arene, acting as a four-connected node, bridges the rare earth cations into a 3D porous MOF in which 1D smaller circular hydrophilic channels and larger quadratic ones are lined up along the c axis and interconnected to each other by the calixarene cavities and other interstices.

Metal-organic frameworks based on the pyridine-2,3-dicarboxylate and a flexible bispyridyl ligand: syntheses, structures, and photoluminescence

Three new metal-organic coordination polymers, [Cu(2,3-pydc)(bpp)]center dot 2.5H(2)O (1), [Zn(2,3-pydc)(bpp)]center dot 2.5H(2)O (2) and [Cd(2,3-pydc)(bpp)(H2O)]center dot 3H(2)O (3) (2,3-pydcH(2) = pyridine-2,3-dicarboxylic acid, bpp 1,3-bis(4-pyridyl)propane), have been synthesized at room temvperature. All complexes have metal ions serving as 4-connected nodes but represent two quite different structural motifs. Complexes 1 and 2 are isomorphous, both of which feature 2D -> 3D parallel interpenetration. Each two-dimensional (2D) layer with (4, 4) topology is interlocked by two nearest neighbours, one above and one below, thus leading to an unusual 3D motif. Complex 3 has a non-interpenetrating 3D CdSO4 framework with cavities occupied by uncoordinated water molecules.

Poly[[diaqua-mu-4,4 '-bipyridine-dinitratodi-mu-L-tyrosinato-dicopper(II)]: a chiral two-dimensional coordination polymer

The title compound, [Cu-2(C9H10NO3)(2)(NO3)(2)(C10H8N2)-(H2O)(2)](n), contains Cu-II atoms and L-tyrosinate (L-tyr) and 4,4'-bipyridine (4,4'-bipy) ligands in a 2:2:1 ratio. Each Cu atom is coordinated by one amino N atom and two carboxylate O atoms from two L-tyr ligands, one N atom from a 4,4'-bipy ligand, a monodentate nitrate ion and a water molecule in an elongated octahedral geometry. Adjacent Cu atoms are bridged by the bidentate carboxylate groups into a chain. These chains are further linked by the bridging 4,4'-bipy ligands, forming an undulated chiral two-dimensional sheet. O-H center dot center dot center dot O and N-H center dot center dot center dot O hydrogen bonds connect the sheets in the [100] direction. This study offers useful information for the engineering of chiral coordination polymers with amino acids and 4,4'-bipy ligands by considering the ratios of the metal ion and organic components.

Influence of metal particle size on the hydrogenation of maleic anhydride over Pd/C catalysts in scCO(2)

Hydrogenation of maleic anhydride (MAH) with Pd/C catalysts in supercritical carbon dioxide (scCO(2)) was investigated. The selectivity for gamma-butyrolactone (GBL) reached 97.3% in scCO(2) at 100% conversion of MAH, which was notably higher than that of 77.4% obtained in organic solvent of ethylene glycol dimethyl ether (EGDME). The particle size of Pd exhibited large influence on the reaction rate and selectivity of GBL. Higher selectivity of GBL was obtained with Pd/C catalyst of smaller Pd particle size, and the rate of GBL selectivity increase as a function of CO2 pressure was found to be significantly correlated with Pd particle size.

Ethylene Polymerization and Ethylene/Hexene Copolymerization with Vanadium(III) Catalysts Bearing Heteroatom-Containing Salicylaldiminato Ligands

A series of novel vanadium(III) complexes hearing heteroatoill-containing group-substituted salicylaldiminato ligands [RN=CH(ArO)]VCl2(THF)(2) (Ar = C6H4, R = C3H2NS, 2a; C7H4NS, 2c; C7H5N2, 2d; Ar = C(6)H(2)tBu(2) (2,4), R = C3H2NS, 2b) have been synthesized and characterized. Structure of complex 2c was further confirmed by X-ray crystallographic analysis. The complexes were investigated as the catalysts for ethylene polymerization in the presence of Et2AlCl. Complexes 2a-d exhibited high catalytic activities (up to 22.8 kg polyethylene/mmolv h bar), and affording polymer with unimodal molecular weight distributions at 25-70 degrees C in the first 5-min polymerization, whereas produced bimodal molecular weight distribution polymers at 70 degrees C when polymerization time prolonged to 30 min. The catalyst structure plays an important role in controlling the molecular weight and molecular weight distribution of the resultant polymers produced in 30 min polymerization. In addition, ethylene/hexene copolymerizations with catalysts 2a-d were also explored in the presence of Et2AlCl, which leads to the high molecular weight and unimodal distributions copolymers with high comonomer incorporation.