Palladium Catalyzed Coupling Reactions: Mechanism of Reductive Elimination. Progress Report, October 1, 1979-September 30, 1980. [Ethane Elimination] (open access)

Palladium Catalyzed Coupling Reactions: Mechanism of Reductive Elimination. Progress Report, October 1, 1979-September 30, 1980. [Ethane Elimination]

The 1,1-reductive elimination of ethane from three cis-bis(phosphine)-dimethylpalladium complexes, L/sub 2/Pd(CH/sub 3/)/sub 2/ (L = PPh/sub 3/, PPh/sub 2/,CH/sub 3/ and L/sub 2/ = Ph/sub 2/PCH/sub 2/CH/sub 2/PPh/sub 2/), and three trans analogs (L = PPh/sub 3/, PPh/sub 2/CH/sub 3/ and L/sub 2/ = 2,11-bis(diphenylphosphinomethyl)benzo(c)phenanthrene (TRANSPHOS)) was carried out. The three cis complexes underwent reductive elimination in the presence of coordinating solvents (DMSO, DMF, and THF). The trans complexes which could isomerize to cis (L = PPh/sub 3/, PPh/sub 2/CH/sub 3/) did so in polar solvents and then underwent reductive elimination. TRANSPHOS dimethylpalladium would not undergo reductive elimination of ethane. The eliminations from the cis isomers were intramolecular and displayed first order kinetics. Although TRANSPHOS dimethylpalladium(II) would not undergo a 1,1-reductive elimination of ethane, the addition of CD/sub 3/I to a DMSO solution of this complex at 25/sup 0/C rapidly produced CD/sub 3/-CH/sub 3/, implicating a transient palladium(IV) intermediate. E- and Z-bromostyrylbis(diphenylmethylphosphine)palladium(0) react with methyl lithium in THF at ambient temperature to give the E- and Z- propenylbenzenes, respectively. At -78/sup 0/C, the intermediate E- and Z-styrylmethylbis(diphenylmethylphosphine)palladium(II) complexes (9a,b) can be isolated. On raising the temperature of solutions of 9a,b in THF, E- and Z-propenylbenzenes are produced. The reductive elimination …
Date: September 1, 1980
Creator: Stille, J. K.
System: The UNT Digital Library
Mean and Peak Wind Load Reduction on Heliostats (open access)

Mean and Peak Wind Load Reduction on Heliostats

This report presents the results of wind-tunnel tests supported through the Solar Energy Research Institute (SERI) by the Office of Solar Thermal Technology of the US Department of Energy as part of the SERI research effort on innovative concentrators. As gravity loads on drive mechanisms are reduced through stretched-membrane technology, the wind-load contribution of the required drive capacity increases in percentage. Reduction of wind loads can provide economy in support structure and heliostat drive. Wind-tunnel tests have been directed at finding methods to reduce wind loads on heliostats. The tests investigated both mean and peak forces, and moments. A significant increase in ability to predict heliostat wind loads and their reduction within a heliostat field was achieved. In addition, a preliminary review of wind loads on parabolic dish collectors was conducted, resulting in a recommended research program for these type collectors. 42 refs., 38 figs., 1 tab.
Date: September 1, 1987
Creator: Peterka, J. A.; Tan, L.; Bienkiewcz, B. & Cermak, J. E.
System: The UNT Digital Library
Palladium Catalyzed Coupling Reactions: Mechanism of Reductive Elimination. Progress Report, June 1, 1978-September 30, 1979 (open access)

Palladium Catalyzed Coupling Reactions: Mechanism of Reductive Elimination. Progress Report, June 1, 1978-September 30, 1979

The coupling reaction of benzyl halides and organolithium, organotin, or Grignard Reagents is catalyzed by palladium. The sequence of events in the catalytic cycle is oxidative addition of the benzyl halide to palladium(0), methathesis by the organometallic reagent to give a benzyl methyl palladium(II) complex, oxidative addition of the benzyl halide to give a palladium(IV) complex, and reductive elimination of benzyl and methyl to give ethylbenzene. The reductive elimination from palladium bearing an optically active ..cap alpha..-deuteriobenzyl group takes place with retention of configuration at carbon, and is therefore concerted or nearly concerted. Since rho is positive in the catalytic reaction with substituted aryl halides, an oxidative addition, probably during the Pd(II) to Pd(IV) reaction, is the slow step in the catalytic cycle. The intermediate diorganopalladium species can be isolated when the two groups attached to palladium are both methyl or methyl and either cis or trans-..beta..-styryl. The decomposition of these species can be followed by NMR. In the case of methylstyrylpalladium(II) complexes, the reductive elimination gives propenyl benzene with stereospecific retention of double bond geometry. Cis-dimethylbis(diphenylmethylphosphine)palladium(II) does not undergo isomerization to the more stable trans isomer in an inert solvent, and is stable toward reductive elimination up to 50/sup …
Date: September 1, 1979
Creator: Stille, J. K.
System: The UNT Digital Library
Evaluation of Aftermarket Fuel Delivery Systems for Natural Gas and Lpg Vehicles (open access)

Evaluation of Aftermarket Fuel Delivery Systems for Natural Gas and Lpg Vehicles

This study was designed to evaluate the effectiveness of aftermarket fuel delivery systems for vehicles fueled by compressed natural gas (CNG) and liquefied petroleum gas (LPG). Most of the CNG and LPG vehicles studied were converted to the alternative fuel after purchase. There are wide variations in the quality of the conversion hardware and the installation. This leads to questions about the overall quality of the converted vehicles, in terms of emissions, safety, and performance. There is a considerable body of emissions data for converted light-duty vehicles, and a smaller amount for medium- and heavy-duty vehicles. However, very few of these data involve real world conditions, and there is growing concern about in-use emissions. This report also attempts to assess factors that could allow in-use emissions to vary from the ``best-case`` results normally reported. The study also addresses issues of fuel supply, fuel composition, performance, safety, and warranty waivers. The report is based on an extensive literature and product survey and on the author`s experience with fuel delivery systems for light-duty vehicles.
Date: September 1, 1992
Creator: Willson, B.
System: The UNT Digital Library
Advanced NMR approaches in the characterization of coal. Final technical report, September 1, 1990--August 31, 1993 (open access)

Advanced NMR approaches in the characterization of coal. Final technical report, September 1, 1990--August 31, 1993

This project addressed two main goals and one much smaller one. The main goals were (1) to improve the significance, reliability and information content in high-resolution NMR (nuclear magnetic resonance) characterization of coal samples and (2) to develop chemically informative NMR imaging techniques for coal. The minor goal was to explore advanced features of dynamic nuclear polarization (DNP) as a technique for coal characterization; this included the development of two DNP probes and the examination of DNP characteristics of various carbonaceous samples, including coals. {sup 13}C NMR advances for coal depended on large-sample MAS devices, employing either cross-polarization (CP) or direct polarization (DP) approaches. CP and DP spin dynamics and their relationships to quantitation and spin counting were elucidated. {sup 1}H NMR studies, based on CRAMPS, dipolar dephasing and saturation with perdeuteropyridine, led to a {sup 1}H NMR-based elucidation of chemical functionality in coal. {sup 1}H and {sup 13}C NMR imaging techniques, based on magic-angle spinning and rotating magnetic field gradients, were developed for introducing chemical shift information (hence, chemical detail) into the spatial imaging of coal. The TREV multiple-pulse sequence was found to be useful in the {sup 1}H CRAMPS imaging of samples like coal.
Date: September 30, 1993
Creator: Maciel, G. E.
System: The UNT Digital Library
Evaluation of Aftermarket Fuel Delivery Systems for Natural Gas and Lpg Vehicles (open access)

Evaluation of Aftermarket Fuel Delivery Systems for Natural Gas and Lpg Vehicles

This study was designed to evaluate the effectiveness of aftermarket fuel delivery systems for vehicles fueled by compressed natural gas (CNG) and liquefied petroleum gas (LPG). Most of the CNG and LPG vehicles studied were converted to the alternative fuel after purchase. There are wide variations in the quality of the conversion hardware and the installation. This leads to questions about the overall quality of the converted vehicles, in terms of emissions, safety, and performance. There is a considerable body of emissions data for converted light-duty vehicles, and a smaller amount for medium- and heavy-duty vehicles. However, very few of these data involve real world conditions, and there is growing concern about in-use emissions. This report also attempts to assess factors that could allow in-use emissions to vary from the best-case'' results normally reported. The study also addresses issues of fuel supply, fuel composition, performance, safety, and warranty waivers. The report is based on an extensive literature and product survey and on the author's experience with fuel delivery systems for light-duty vehicles.
Date: September 1, 1992
Creator: Willson, B. (Colorado State Univ., Fort Collins, CO (United States))
System: The UNT Digital Library