Catalytically Active Gold Nanomaterials Stabilized by N-heterocyclic Carbenes

Solid supported or ligand capped gold nanomaterials (AuNMs) emerged as versatile and recyclable heterogeneous catalysts for a broad variety of conversions in the ongoing catalytic ′gold rush′. Existing at the border of homogeneous and heterogeneous catalysis, AuNMs offer the potential to merge high catalytic activity with significant substrate selectivity. Owing to their strong binding towards the surface atoms of AuMNs, NHCs offer tunable activation of surface atoms while maintaining selectivity and stability of the NM even under challenging conditions. This work summarizes well-defined catalytically active NHC capped AuNMs including spherical nanoparticles and atom-precise nanoclusters as well as the important NHC design choices towards activity and (stereo-)selectivity enhancements.     

On the holomorphic extension of CR functions from non-generic CR submanifolds of ? n

We give a holomorphic extension result for continuous CR functions on a non-generic CR submanifold N of ℂ ⁿ to complex transversal wedges with edges containing N. We show that given any v∈ℂ ⁿ ∖(T _p N+iT _p N), there exists a wedge of direction v whose edge contains a neighborhood of p in N, such that any continuous CR function defined locally near p extends holomorphically to that wedge.     

Synthesis and structure determination of a stable organometallic uranium(v) imine complex and its isolobal anionic U(IV)-ate complex

The reaction of one equivalent of Cp*₂UCl₂ with 2-(trimethylsilylimino)-1,3-di-tert-butylimidazoline in boiling toluene afforded a one electron oxidation of the uranium metal and the opening of the N-heterocyclic ring, resulting in the formation of an organometallic uranium(V) imine complex. This complex crystallized with one molecule of toluene in the unit cell, and its solid-state structure was determined by X-ray diffraction analysis. When the same reaction was performed in perdeuterated toluene, a myriad of organometallic complexes were obtained, however, when equimolar amounts of water were used in toluene, the same complex was obtained, and its solid state characterization shows two independent molecules in the unit cell with an additional water molecule. For comparison of the geometric parameters, the corresponding isolobal anionic uranium(IV) complex [Cp*₂UCl₃]^? was synthesized by the reaction of Cp*₂UCl₂ with 1,3-di-tert-butylimidazolium chloride, and the resulting U(IV)-ate complex was characterized by X-ray diffraction analysis.     

Experimental investigation of the energy and depth dependence of flux peaking

The yield of helium ions backscattered from Yb implanted in silicon crystals has been studied as a function of the angle between the incident beam direction and various symmetry axes of the silicon crystal. The depth of the implanted Yb has been varied by using different implantation energies, and the analyzing beam energy has been varied from 0.5 to 2 MeV in an effort to obtain information about the energy and depth dependence of the flux-peaking phenomenon. The results are compared with those of Andersen and coworkers. We have observed the oscillation with depth of the flux in the center of a channel predicted by Van Vliet.     

Capillary gas chromatography of monosubstituted cyclopentenes and cyclohexenes

Summary Regularities in the variation of retention indices (I) and index increments (δI/°C, H, ΔI) of monosubstituted cyclopentenes and cyclohexenes with molecular structure on various liquid phases are discussed. An equation for the linear dependence of I on the carbon number is given. Differences in gas chromatographic characteristics between 1- and 3-isomers are more pronounced in the n-alkylcyclopentene series. In the n-alkylcyclohexene series extension of the side chain and increase of column temperature lead to the inversion of the elution order of 1-and 3-isomers. The temperature increments of I for cyclenes are markedly greater than those for open chain hydrocarbons (n-alkenes, n-alkynes).     

Synthesis and characterization of new thorium and uranium phenolate complexes

The reaction between the chelating amino bisphenole ligand (ONOO)H₂ (1) and (ONNO)H₂ (2) with an excess of NaH gives the corresponding bis-sodium salts 3 and 4 quantitatively.The salts were reacted with thorium tetrachloride at room temperature to obtain the corresponding (ONOO)ThCl₂ (5) and (ONNO)ThCl₂ (6) complexes.However, ThCl₄ and UCl₄ react with (3) at higher temperatures to give the corresponding isomorphous homoleptic complexes (ONOO)₂Th (7) and (ONOO)₂U (8).We have also synthesized and characterized a thorium salicylaldiminato complex L₃ThCl (11) , in order to study the effect of the bridged ligand on the molecular structure.     

Polymerization of propylene by mixed Ziegler–Natta and metallocene catalysts

The polymerization of propylene using a mixture of racemic metallocenes and Ziegler–Natta catalysts was investigated. The polypropylene was obtained as a mixture of a fine powder and beads, with the powder being absorbed partially on the beads. The relative amount of the powder can be controlled by the concentration of the metallocene. The compatibility between the components of the mixed catalytic systems and the effect of the components on the rate of polymerization and on the properties of the new polymers were studied. The metallocene system dramatically affects the melt viscosity, isotacticity and molecular weight of the polymers. The two catalytic systems are able to act jointly, producing different polymers, for which separate melting and crystallization temperatures are obtained. © 1998 John Wiley & Sons, Ltd.     

Polymerization of propylene by metallocene and Ziegler–Natta mixed catalytic systems. Study of polypropylene properties

Propylene was polymerized with metallocene and Ziegler–Natta mixed-catalytic systems to obtain reactor blends of metallocene and Ziegler–Natta-derived propylene homopolymers. The two catalytic systems are able to act jointly, providing individual polymers with different melting and crystallization temperatures. Compatibility between the components of the mixed-catalytic systems and the influence of the components on the polymerization process and on the properties of the reactor blends were studied. Thermal, mechanical, viscoelastic, rheological, and optical properties of the blends were tested and compared with those of conventional polypropylene grades. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 3063–3072, 1998