Regioselective Intermolecular Coupling Reaction of Arylketones and Alkenes Involving C-H Bond Activation Catalyzed by an \u3cem\u3ein Situ\u3c/em\u3e Formed Cationic Ruthenium-Hydride Complex

The cationic ruthenium hydride complex, formed in situ from the treatment of the tetranuclear ruthenium hydride complex {[(PCy3)(CO)RuH]4(μ4-O)(μ3-OH)(μ2-OH)} with HBF4·OEt2, was found to be a highly effective catalyst for the intermolecular coupling reaction of arylketones and 1-alkenes to give the substituted indene and ortho-C−H insertion products. The formation of the indene products resulted from the initial alkene isomerization followed by regioselective ortho-C−H insertion of 2-alkene and dehydrative cyclization. The preliminary mechanistic studies revealed a rapid and reversible ortho-C−H bond activation followed by the rate-limiting C−C bond formation step for the coupling reaction

Efficient Dehydrogenation of Amines and Carbonyl Compounds Catalyzed by a Tetranuclear Ruthenium-μ-oxo-μ-hydroxo-hydride Complex

The tetranuclear ruthenium-μ-oxo-μ-hydroxo-hydride complex {[(PCy3)(CO)RuH]4(μ4-O)(μ3-OH)(μ2-OH)} (1) was found to be a highly effective catalyst for the transfer dehydrogenation of amines and carbonyl compounds. For example, the initial turnover rate of the dehydrogenation of 2-methylindoline was measured to be 1.9 s−1 with a TON of 7950 after 1 h at 200 °C. The extensive H/D scrambling patterns observed from the dehydrogenation reaction of indoline-N-d1 and indoline-α-d2 suggest a monohydride mechanistic pathway with the C−H bond activation rate-limiting step

Chain-Selective and Regioselective Ethylene and Styrene Dimerization Reactions Catalyzed by a Well-Defined Cationic Ruthenium-Hydride Complex: New Insights on the Styrene Dimerization Mechanism

The cationic ruthenium hydride complex [(η6-C6H6)(PCy3)(CO)RuH]+BF4− was found to be a highly regioselective catalyst for the ethylene dimerization reaction to give 2-butene products (TOF = 1910 h−1, \u3e95% selectivity for 2-butenes). The dimerization of styrene exclusively produced the head-to-tail dimer (E)-PhCH(CH3)CH═CHPh at an initial turnover rate of 2300 h−1. A rapid and extensive H/D exchange between the vinyl hydrogens of styrene-d8 and 4-methoxystyrene was observed within 10 min without forming the dimer products at room temperature. The inverse deuterium isotope effect of kH/kD = 0.77 ± 0.10 was measured from the first-order plots on the dimerization reaction of styrene and styrene-d8 in chlorobenzene at 70 °C. The pronounced carbon isotope effect on both vinyl carbons of styrene as measured by using Singleton’s method (13C(recovered)/13C(virgin) at C1 = 1.096 and C2 = 1.042) indicates that the C−C bond formation is the rate-limiting step for the dimerization reaction. The Eyring plot of the dimerization of styrene in the temperature range of 50−90 °C led to ΔH⧧ = 3.3(6) kcal/mol and ΔS⧧ = −35.5(7) eu. An electrophilic addition mechanism has been proposed for the dimerization of styrene

Intermolecular Dehydrative Coupling Reaction of Arylketones with Cyclic Alkenes Catalyzed by a Well-Defined Cationic Ruthenium-Hydride Complex: A Novel Ketone Olefination Method via Vinyl C–H Bond Activation

The cationic ruthenium−hydride complex [(η6-C6H6)(PCy3)(CO)RuH]+BF4− was found to be a highly effective catalyst for the intermolecular olefination reaction of aryl ketones with cycloalkenes. The preliminary mechanistic analysis revealed that an electrophilic ruthenium−vinyl complex is the key species for mediating both vinyl C−H bond activation and the dehydrative olefination steps of the coupling reaction

Aqueous Phase C-H Bond Oxidation Reaction of Arylalkanes Catalyzed by a Water-Soluble Cationic Ru(III) Complex [(pymox-Me\u3csub\u3e2\u3c/sub\u3e)\u3csub\u3e2\u3c/sub\u3eRuCl\u3csub\u3e2\u3c/sub\u3e]\u3csup\u3e+\u3c/sup\u3eBF\u3csub\u3e4\u3c/sub\u3e\u3csup\u3e-\u3c/sup\u3e

The cationic complex [(pymox-Me2)RuCl2]+BF4− was found to be a highly effective catalyst for the C−H bond oxidation reaction of arylalkanes in water. For example, the treatment of ethylbenzene (1.0 mmol) with t-BuOOH (3.0 mmol) and 1.0 mol % of the Ru catalyst in water (3 mL) cleanly produced PhCOCH3 at room temperature. Both a large kinetic isotope effect (kH/kD = 14) and a relatively large Hammett value (ρ = −1.1) suggest a solvent-caged oxygen rebounding mechanism via a Ru(IV)-oxo intermediate species

Epitaxial growth and the magnetic properties of orthorhombic YTiO3 thin films

High-quality YTiO3 thin films were grown on LaAlO3 (110) substrates at low oxygen pressures (<10-8 Torr) using pulsed laser deposition. The in-plane asymmetric atomic arrangements at the substrate surface allowed us to grow epitaxial YTiO3 thin films, which have an orthorhombic crystal structure with quite different a- and b-axes lattice constants. The YTiO3 film exhibited a clear ferromagnetic transition at 30 K with a saturation magnetization of about 0.7 uB/Ti. The magnetic easy axis was found to be along the [1-10] direction of the substrate, which differs from the single crystal easy axis direction, i.e., [001].Comment: 14 pages, 4 figure

Predictability of reset switching voltages in unipolar resistance switching

In unipolar resistance switching of NiO capacitors, Joule heating in the conducting channels should cause a strong nonlinearity in the low resistance state current-voltage (I-V) curves. Due to the percolating nature of the conducting channels, the reset current IR, can be scaled to the nonlinear coefficient Bo of the I-V curves. This scaling relationship can be used to predict reset voltages, independent of NiO capacitor size; it can also be applied to TiO2 and FeOy capacitors. Using this relation, we developed an error correction scheme to provide a clear window for separating reset and set voltages in memory operations

Direct observation of the proliferation of ferroelectric loop domains and vortex-antivortex pairs

We discovered "stripe" patterns of trimerization-ferroelectric domains in hexagonal REMnO3 (RE=Ho, ---, Lu) crystals (grown below ferroelectric transition temperatures (Tc), reaching up to 1435 oC), in contrast with the vortex patterns in YMnO3. These stripe patterns roughen with the appearance of numerous loop domains through thermal annealing just below Tc, but the stripe domain patterns turn to vortex-antivortex domain patterns through a freezing process when crystals cross Tc even though the phase transition appears not to be Kosterlitz-Thouless-type. The experimental systematics are compared with the results of our six-state clock model simulation and also the Kibble-Zurek Mechanism for trapped topological defects

Determination of Dynamic Shear Modulus of Soils from Static Strength

A correlation study between the dynamic shear modulus obtained from the resonant column technique and the static strength obtained from the undrained triaxial compression test is described. The materials studied were a uniform sand, a non-active fine silty clay and a highly-active bentonite clay treated with additives to increase the range for static and dynamic shear strength of the soils. It is noted that a linear relationship exists between the dynamic shear modulus, except for those soil specimens having very low strength, independent of test parameters. Using linear regression analysis, empirical equations for predicting the maximum dynamic shear modulus from the static strength have been obtained for the three different soils