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Thermosonic flip chip interconnection using electroplated copper column arrays
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Regioselective Formation of α-Vinylpyrroles from the Ruthenium-Catalyzed Coupling Reaction of Pyrroles and Terminal Alkynes Involving C–H Bond Activation
The cationic ruthenium catalyst Ru3(CO)12/NH4PF6 was found to be highly effective for the intermolecular coupling reaction of pyrroles and terminal alkynes to give gem-selective α-vinylpyrroles. The carbon isotope effect on the α-pyrrole carbon and the Hammett correlation from a series of para-substituted N-arylpyrroles (ρ = −0.90) indicate a rate-limiting C−C bond formation step of the coupling reaction
Scope and Mechanistic Investigations on the Solvent-Controlled Regio- and Stereoselective Formation of Enol Esters from the Ruthenium-Catalyzed Coupling Reaction of Terminal Alkynes and Carboxylic Acids
The ruthenium-hydride complex (PCy3)2(CO)RuHCl was found to be a highly effective catalyst for the alkyne-to-carboxylic acid coupling reaction to give synthetically useful enol ester products. A strong solvent effect was observed for the ruthenium catalyst in modulating the activity and selectivity; the coupling reaction in CH2Cl2 led to the regioselective formation of gem-enol ester products, while the stereoselective formation of (Z)-enol esters was obtained in THF. The coupling reaction was found to be strongly inhibited by PCy3. The coupling reaction of both PhCO2H/PhC≡CD and PhCO2D/PhC≡CH led to extensive deuterium incorporation on the vinyl positions of the enol ester products. An opposite Hammett value was observed when the correlation of a series of para-substituted p-X-C6H4CO2H (X = OMe, CH3, H, CF3, CN) with phenylacetylene was examined in CDCl3 (ρ = +0.30) and THF (ρ = −0.68). Catalytically relevant Ru-carboxylate and -vinylidene-carboxylate complexes, (PCy3)2(CO)(Cl)Ru(κ2-O2CC6H4-p-OMe) and (PCy3)2(CO)(Cl)RuC(═CHPh)O2CC6H4-p-OMe, were isolated, and the structure of both complexes was completely established by X-ray crystallography. A detailed mechanism of the coupling reaction involving a rate-limiting C−O bond formation step was proposed on the basis of these kinetic and structural studies. The regioselective formation of the gem-enol ester products in CH2Cl2 was rationalized by a direct migratory insertion of the terminal alkyne via a Ru-carboxylate species, whereas the stereoselective formation of (Z)-enol ester products in THF was explained by invoking a Ru-vinylidene species
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Modeling and analysis of the variability of the water cycle in the upper Rio Grande basin at high resolution
Estimating the water budgets in a small-scale basin is a challenge, especially in the mountainous western United States, where the terrain is complex and observational data in the mountain areas are sparse. This manuscript reports on research that downscaled 5-yr (1999-2004) hydrometeorological fields over the upper Rio Grande basin from a 2.5° NCEP-NCAR reanalysis to a 4-km local scale using a regional climate model [fifth-generation Pennsylvania State University-National Center for Atmospheric Research Mesoscale Model (MM5), version 3]. The model can reproduce the terrain-related precipitation distribution - the trend of diurnal, seasonal, and interannual precipitation variability - although poor snow simulation caused it to overestimate precipitation and evapotranspiration in the cold season. The outcomes from the coupled model are also comparable to offline Variable Infiltration Capacity (VIC) and Land Data Assimilation System (LDAS)/Mosaic land surface simulations that are driven by observed and/or analyzed surface meteorological data. © 2007 American Meteorological Society
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