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
Novel Concepts in Electrochemical Solar Cells. Third Quarterly Progress Report, November 15, 1979-January 15, 1980. [Molten Salt Electrolytes] (open access)

Novel Concepts in Electrochemical Solar Cells. Third Quarterly Progress Report, November 15, 1979-January 15, 1980. [Molten Salt Electrolytes]

Efforts have been primarily directed toward evaluation of the room temperature molten salt electrolyte in terms of its overall performance for photovoltaic cells. Mass transport processes may prove to be the rate-limiting factor for such electrolytes, unless the concentration of the photo-active redox component can be increased and the solvent viscosity reduced. Acid-base surface chemistry of n-GaAs as occurs in aqueous systems, has been found present and its consequences will be further explored. The selection and optimization of PEC electrolytes is a complex task and we believe that a systems approach would facilitate in identifying the basic electrolyte properties needed. A preliminary analysis reveals that although some of the criteria for an electrolyte are definable precisely, others do require empirical experimentation. It can be concluded that relatively few electrolytes in current use are adequate and it would appear that greater efforts to develop electrolytes would be advantageous. The various types of electrolytes that could be used for PEC's have been identified. Good quality MoSe/sub 2/ single crystals can be grown and short circuit currents greater than previously reported have been achieved in an I/sub 2//I/sup -//Pt cell. A novel technique to produce photo-active films by anodization is being investigated, initially …
Date: January 1, 1980
Creator: DuBow, J.; Job, R. & Krishnan, R.
System: The UNT Digital Library
Variability Within the Ocean-Atmospheric System Over the North Pacific (open access)

Variability Within the Ocean-Atmospheric System Over the North Pacific

Characteristics of the oceanic mixed layer over the North Pacific were examined utilizing a number of statistical methods. Based on the analyses of twelve years of data, a quasi-meridional differentiation (QMD) in sea surface temperature (SST) spectra across the North Pacific was observed. The SST spectra became increasingly red as an increasing function of latitude. A strong 21 to 26 day cycle in SST anomalies is discussed which may be a reflection of heat fluxes. These fluxes also vacillate significantly on this time-scale in conjunction with cycles observed in the atmospheric energy modes of available potential and kinetic energy. Examination of an oceanic heat budget on a spatial and temporal basis suggest that the impact of latent and sensible heat fluxes upon ..delta..SST is partially a function of the magnitude of the heat fluxes as well as of the depth to which their effects are mixed. The heat budget analyses and the fitting of power spectra of SST anomalies over the North Pacific to a two-parameter oceanic model, suggest that SST behavior over the mid-oceanic regions of the North Pacific is dominated by the influence of latent and sensible heat fluxes. On the other hand, over the remainder of the …
Date: January 1, 1980
Creator: Ciesielski, P E
System: The UNT Digital Library
Cross-Spectral Study of the Spatial Relationships in the North Pacific Sea-Surface Temperature Anomaly Field. Report No. 23 (open access)

Cross-Spectral Study of the Spatial Relationships in the North Pacific Sea-Surface Temperature Anomaly Field. Report No. 23

Cross-spectral analysis is used to examine the dependence of the temporal covariation of sea-surface temperature (SST) anomalies at pairs of spatially separated points in the North Pacific on (1) the time scale of the variations, (2) the relative displacement of the points and (3) their location within the North Pacific basin. Spatial scales considered here range from 1000 kilometers up to the width of the basin. The study focuses on cross-spectral estimates for the interannual frequency band, 0.125-0.75 yr/sup -1/ although estimates for three other bands spanning higher frequencies are also examined.
Date: March 1, 1980
Creator: Middleton, John W.
System: The UNT Digital Library