ansa-Metallocene derivatives XXXIII. 2-Dimethylamino-substituted bis-indenyl zirconium dichloride complexes with and without a dimethylsilyl bridge: syntheses, crystal structures and properties in propene polymerization catalysis

Bis(2-N,N-dimethylamino-indenyl) zirconium dichloride, (2-(CH₃)₂N-C₉H₆)₂ZrCl₂, and dimethylsilyl-bridged bis(2-N,N-dimethylamino-indenyl) zirconium dichloride, (CH₃)₂Si(2-(CH₃)₂N-C₉H₅)₂ZrCl₂, were prepared by reaction of the corresponding ligand lithium salts with ZrCl₄ in toluene. Diffractometric structure determinations reveal C₂-symmetric complex geometries for both complexes. An increased electron density at the Zr center of the dimethylamino-substituted complexes is indicated by reduction potentials which are 0.3–0.4 V more negative than those of their unsubstituted analogs. When activated with methyl aluminoxane in toluene solution, (CH₃)₂Si(2-(CH₃)₂N-C₉H₅)₂ZrCl₂ catalyzes the polymerization of propene to polymers with a microstructure comparable with that of polymers produced with other Me₂Si-bridged bis(indenyl)ZrCl₂ complexes, but with a substantially increased fraction of i-propyl end groups derived from alkyl exchange between Zr-polymer and Al---Me species.     

Intramolecular metal—double bond interactions : VII. Intramolecular cyclization of alkenyl derivatives of lithium,aluminum, gallium and indium

The intramolecular cyclization reactions of tri-1-hex-5-enyl Group III derivatives and of 1-hex-5-enyllithium have been investigated and it is proposed that the reactions may be depicted as internal addition across the terminal double bonds of the alkenyl species. The cyclization reaction proceeds more readily for the 1-hex-5-enyl derivatives than for any other chain length and is dependent on temperature, concentration and solvent. ¹H NMR data and cryoscopic molecular weight data are presented for several diisobutyialkenyl- and diisobutylalkyl-aluminum derivatives. These data have been interpreted in terms of a direct intramolecular interaction between the metal center and the π-electron system of the olefinic site. The intramolecular cyclization reactions for the 1-hept-6-enyl, 1-oct-7-enyl- and 1-undec-10-enylaluminum derivatives also were investigated and it was found that cyclization occurred only for the 1-hept-6-enyl derivative.     

Thermoresponsive nanostructures by self-assembly of a poly(N-isopropylacrylamide)-lipid conjugate

The synthesis and purification of a poly(N-isopropylacrylamide)-lipid conjugate and its use in the preparation of a thermoresponsive lipid mesophase is described. Specifically, poly(N-isopropylacrylamide) with a single carboxyl group at one end was activated with dicyclohexylcarbodiimide/N-hydroxysuccinimide to form an active ester. This N-hydroxysuccinimide ester was then used to form a dimyristoyl-sn-glycero-3-phosphoethanolamine conjugate with poly(N-isopropylacrylamide) via an amide bond, rendering the conjugate amphiphilic. Quaternary phases comprising the conjugate, a phosopholipid, dimyristoylphosphatidylcholine, and a cosurfactant, N,N-dimethyldodecylamine-N-oxide, dispersed in water were found to self-assemble at room temperature to form liquid crystalline gels, adopting an expanded lamellar structure. A modest increase in temperature triggered the reversible conversion of the aggregate to a collapsed lamellar structure, while a modest reduction in temperature resulted in its conversion to a nonlamellar phase. The phases were characterized by polarized optical microscopy and small-angle X-ray scattering (SAXS).     

Development of a multiplex microarray microsystem

A hybrid multiplex microarray microsystem has been developed that consists of 32 individually addressable array reaction chambers, supporting the use of multichannel pipettes for addition of up to 8 samples simultaneously. Discrimination between Campylobacter jejuni and Campylobacter coli bacteria was observed in DNA samples containing Campylobacter spp., with the same specificity and sensitivity as when compared to a full-size microarray. The spinloaded multiplex microarray microsystem described provides a novel and convenient test format for simultaneous low-density microarray analysis and is universally adaptable to other DNA, protein or small molecule microarray based applications.     

Concise total syntheses of the bioactive mesotricyclic diterpenoids jatrophatrione and citlalitrione

The highly functionalized [5.9.5] tricyclic framework resident in jatrophatrione (1) and citlalitrione (2) has been synthesized. The route begins with the tandem anionic oxy-Cope rearrangement/methylation/transannular ene cyclization of 21 and subsequent introduction of a conjugated enone double bond. Hydroxyl-directed 1,4-reduction of this functionality in 25 with LiAlH(4)/CuI/hexamethylphosphoramide/tetrahydrofuran sets the stage for the implementation of a Grob fragmentation and expedited generation of 27. Stereocontrolled intramolecular hydrosilylation allows for the subsequent introduction of a cyclic carbonate as in 53. This intermediate undergoes remarkably efficient, fully regiocontrolled Treibs reaction to generate 54, with this maneuver serving as a pivotal step for making 1 available five steps later. Treatment of 1 with m-chloroperbenzoic acid leads to 2, with attack occurring preferentially on a alpha-face of the double bond more remote to the carbonyl.     

Über die Systeme AJ/CoJ2 und die kristallchemischen Beziehungen in der Gruppe der Doppelhalogenide AnCoX(n+2) mit X = Cl,Br, J [1]

The Systems AI/CoI₂ (A = Alkali Metal, Tl, Ag) and the Crystal Chemistry of the Double Halides A_nCoX_(n+2) with X = Cl, Br, I The systems AI/CoI₂ (A = Cs, Rb, K, Tl, Na, Ag) were investigated by differencethermal analysis. The systems of NaI and AgI are found to be eutectical. A compound A₂CoI₄ always exists in the other systems. Cs₂CoI₄ crystallizes in the β-K₂SO₄ type with a coordination number (C.N.) for Cs equal to 9/10. Results obtained with single crystal technique reveal for the first time that among the double halides Rb₂CoI₄ is of the monoclinic Sr₂GeS₄ type (C. N. for Rb = 6(+2)). The compounds K₂CoJ₄, Tl₂CoJ₄, T-K₂CoBr₄, and T-Tl₂CoBr₄ are isotypic. Both structure groups are characterized by isolated CoX₄^2? tetrahedra. Reflectance spectra and magnetic susceptibilities can be explained on the basis of crystal field theory. – Our results close presently existing gaps in the knowledge on systems of CoBr₂ and CoCl₂ too.     

A new class of C1-symmetric monosulfoximine ligands for enantioselective hetero Diels-Alder reactions

Quinoline-based C1-symmetric sulfoximines have been used as chiral ligands in copper-catalyzed asymmetric hetero Diels-Alder reactions leading to cycloadducts with up to 96% ee.     

Anomalous grazing incidence small-angle x-ray scattering studies of platinum nanoparticles formed by cluster deposition

The size evolution of platinum nanoparticles formed on a SiO2/Si(111) substrate as a function of the level of surface coverage with deposited clusters has been investigated. The anisotropic shapes of sub-nanometer-size nanoparticles are changed to isotropic on the amorphous substrate as their sizes increased. Using anomalous grazing incidence small-angle x-ray scattering (AGISAXS), the scattering from nanoparticles on the surface of a substrate is well separated from that of surface roughness and fluorescence. We show that AGISAXS is a very effective method to subtract the background and can provide unbiased information about particle sizes of less than 1 nm.     

Influence of initial oxygen coverage and magnetic moment on the NO decomposition on rhodium (111)

In this study, density functional theory calculations were performed to investigate the influence of oxygen preoccupation on the nitrogen oxide decomposition on rhodium. Besides gauging the coverage dependence of the adsorption energy of NO on the (111) rhodium facet, the influence of the initial oxygen coverage on the kinetics and thermodynamics of the nitrogen oxide decomposition reaction was also studied. The results are discussed with respect to a novel NOx decomposition catalyst. Furthermore, the influence of spin effects on the adsorption geometry as well as the adsorption energy is examined. It will be addressed why spin effects only have a minor influence on the behavior of NO on a rhodium surface.     

Ein isoperiboles lösungskalorimeter zur messung von lösungsenthalpien der doppelchloride des magnesiums

For measuring solution enthalpies of the strong hygroscopic double chlorides, an isoperibol solution calorimeter was built. Samples of 2–5 g could be solved to a molar dilution 1 : 3000. The temperature difference between reaction vessel and thermostat was measured by a thermopile; the temperature of the thermostat was constant to 2 · 10^?4°C. From the molar enthalpies of solution (ΔH^L), enthalpies for the reactions nACl + MCl₂ = A_sMCl(_{s + 2}) were calculated: ΔHP^R = ? ΔH^L (double chloride) + ΔH^L(n Cl) + ΔH^L(MCL₂) These values are relatively small: about ? 50 kJ for the Cs-compounds, nearly zero for the K- and Na-compounds.