2,699 Matching Results

Search Results

Advanced search parameters have been applied.

INTERPRETATION OF RAYLEIGH SCATTERING IN A FLAME

Description: Rayleigh scattering has become an accepted technique for the determination of total number density during the combustion process. The interpretation of the ratio of total Rayleigh scattering signal as a ratio of densities or temperatures is hampered by the changing composition and mean molecular weight through a flame. Typical values of correction factors as a function of degree of reaction, fuel, and equivalence ratio are calculated for an idealized one-dimensional flame front. The fuels considered are H{{sub 2}, CH{sub 4}, C{sub 2}H{sub 4}, C{sub 2}H{sub 6}, and C{sub 3}H{sub 8}. Errors of up to 30% can occur in the interpretation of the Rayleigh scattering as gas density for the heavier hydrocarbon fuels due, primarily, to the presence of CO as an intermediate combustion product. Conversely, using H{sub 2} as a fuel will result in a maximum error of 3%, which is within the expected experimental accuracy of a typical Rayleigh scatterinq system. The interpretation of Rayleigh scattering as temperature was found to have larger errors than the interpretation as density. Nevertheless, when corrections are applied for changes in gas composition, Rayleigh scattering provides an excellent measure of total gas density and temperature in flames.
Date: April 1, 1980
Creator: Namer, I.; Schefer, R.W. & Chan, M.
Partner: UNT Libraries Government Documents Department

PHOTOCHEMICAL AND NON-PHOTOCHEMICAL HOLE BURNING IN DIMETHYL-S-TETRAZINE IN A POLYVINYL CARBAZOLE FILM

Description: Hole burning as well as fluorescence line narrowing experiments have been performed on the system dimethyl-s-tetrazine in polyvinyl carbazole films at low temperatures. The first singlet electronic absorption bands are typical (300 cm{sup -1} wide) of inhomogeneously broadened bands of guest molecules in amorphous organic hosts. Evidence is presented for both photochemical and non-photochemical hole burning. The narrowest holes observed were Lorentzian, had a width 0.44 cm{sup -1} at 1.8 K, and are believed to be of non-photochemical origin. A model which envisions the guest molecules to occupy different sites in the polymer host with a distribution of energy barriers between sites is used to describe these observations. The fast (20 psec) relaxation time implied by the 0,44 cm{sup -1} Lorentzian linewidth is interpreted as indicative of the rate of site interconversion in the excited state.
Date: May 1, 1980
Creator: Cuellar, E. & Castro, G.
Partner: UNT Libraries Government Documents Department

Laboratory Studies of the Reactive Chemistry and Changing CCN Properties of Secondary Organic Aerosol, Including Model Development

Description: The chemical evolution of secondary-organic-aerosol (SOA) particles and how this evolution alters their cloud-nucleating properties were studied. Simplified forms of full Koehler theory were targeted, specifically forms that contain only those aspects essential to describing the laboratory observations, because of the requirement to minimize computational burden for use in integrated climate and chemistry models. The associated data analysis and interpretation have therefore focused on model development in the framework of modified kappa-Koehler theory. Kappa is a single parameter describing effective hygroscopicity, grouping together several separate physicochemical parameters (e.g., molar volume, surface tension, and van't Hoff factor) that otherwise must be tracked and evaluated in an iterative full-Koehler equation in a large-scale model. A major finding of the project was that secondary organic materials produced by the oxidation of a range of biogenic volatile organic compounds for diverse conditions have kappa values bracketed in the range of 0.10 +/- 0.05. In these same experiments, somewhat incongruently there was significant chemical variation in the secondary organic material, especially oxidation state, as was indicated by changes in the particle mass spectra. Taken together, these findings then support the use of kappa as a simplified yet accurate general parameter to represent the CCN activation of secondary organic material in large-scale atmospheric and climate models, thereby greatly reducing the computational burden while simultaneously including the most recent mechanistic findings of laboratory studies.
Date: January 31, 2013
Creator: Martin, Scot
Partner: UNT Libraries Government Documents Department

The generation of efficient supported (Heterogeneous) olefin metathesis catalysts

Description: Over the past decade, a new family of homogeneous metathesis catalysts has been developed that will tolerate most organic functionalities as well as water and air. These homogeneous catalysts are finding numerous applications in the pharmaceutical industry as well as in the production of functional polymers. In addition the catalysts are being used to convert seed oils into products that can substitute for those that are now made from petroleum products. Seed oils are unsaturated, contain double bonds, and are a ready source of linear hydrocarbon fragments that are specifically functionalized. To increase the number of applications in the area of biomaterial conversion to petrol chemicals, the activity and efficiency of the catalysts need to be as high as possible. The higher the efficiency of the catalysts, the lower the cost of the conversion and a larger number of practical applications become available. Active supported catalysts were prepared and tested in the conversion of seed oils and other important starting materials. The outcome of the work was successful and the technology has been transferred to a commercial operation to develop viable applications of the discovered systems. A biorefinery that converts seed oils is under construction in Indonesia. The catalysts developed in this study will be considered for the next generation of operations.
Date: April 5, 2013
Creator: Grubbs, Robert H.
Partner: UNT Libraries Government Documents Department

Feet on the potential energy surface, head in the pie clouds

Description: This work presents explorations of the potential energy surface of clusters of atoms and of the interactions between molecules. First, structures of small aluminum clusters are examined and classified as ground states, transition states, or higher-order saddle points. Subsequently, the focus shifts to dispersion-dominated π-π interactions when the potential energy surfaces of benzene, substituted benzene, and pyridine dimers are explored. Because DNA nucleotide bases can be thought of as substituted heterocycles, a natural extension of the substituted benzene and pyridine investigations is to model paired nucleotide bases. Finally, the success of the dispersion studies inspires the development of an extension to the computational method used, which will enable the dispersion energy to be modeled – and the potential energy surface explored – in additional chemical systems. The effective fragment potential (EFP) method is described, as well as various quantum mechanical methods. An ab inito quantum mechanical study of 13-atom aluminum clusters is described. EFP studies of aromatic dimers are reported in which dispersion energy makes a significant contribution to the attraction between monomers. Theory and code development toward a means of computing dispersion energy in mixed ab inito-EFP systems are described.
Date: July 12, 2012
Creator: Smith, Quentin
Partner: UNT Libraries Government Documents Department

Cellulose and cellobiose: adventures of a wandering organic chemist in theoretical chemistry

Description: The energies arising from the rotation of free hydroxyl groups in the central glucose residue of a cellulose crystalline assembly, calculated using RHF, DFT, and FMO2/MP2 methods, will be presented. In addition, interactions of this central glucose residue with some of the surrounding residues (selected on the basis of the interaction strengths) are analyzed. The mechanism of acid-catalyzed hydrolysis of cellobiose, which is the repeating unit of cellulose. Energies corresponding to the different steps of this mechanism calculated using RHF and DFT are compared with those previously reported using molecular dynamics calculations and with experimental data.
Date: April 3, 2012
Creator: Baluyut, John
Partner: UNT Libraries Government Documents Department

Bulk gold catalyzed oxidation reactions of amines and isocyanides and iron porphyrin catalyzed N-H and O-H bond insertion/cyclization reactions of diamines and aminoalcohols

Description: This work involves two projects. The first project entails the study of bulk gold as a catalyst in oxidation reactions of isocyanides and amines. The main goal of this project was to study the activation and reactions of molecules at metal surfaces in order to assess how organometallic principles for homogeneous processes apply to heterogeneous catalysis. Since previous work had used oxygen as an oxidant in bulk gold catalyzed reactions, the generality of gold catalysis with other oxidants was examined. Amine N-oxides were chosen for study, due to their properties and use in the oxidation of carbonyl ligands in organometallic complexes. When amine N-oxides were used as an oxidant in the reaction of isocyanides with amines, the system was able to produce ureas from a variety of isocyanides, amines, and amine N-oxides. In addition, the rate was found to generally increase as the amine N-oxide concentration increased, and decrease with increased concentrations of the amine. Mechanistic studies revealed that the reaction likely involves transfer of an oxygen atom from the amine N-oxide to the adsorbed isocyanide to generate an isocyanate intermediate. Subsequent nucleophilic attack by the amine yields the urea. This is in contrast to the bulk gold-catalyzed reaction mechanism of isocyanides with amines and oxygen. Formation of urea in this case was proposed to proceed through a diaminocarbene intermediate. Moreover, formation of the proposed isocyanate intermediate is consistent with the reactions of metal carbonyl ligands, which are isoelectronic to isocyanides. Nucleophilic attack at coordinated CO by amine N-oxides produces CO{sub 2} and is analogous to the production of an isocyanate in this gold system. When the bulk gold-catalyzed oxidative dehydrogenation of amines was examined with amine N-oxides, the same products were afforded as when O{sub 2} was used as the oxidant. When the two types of oxidants were directly ...
Date: December 29, 2011
Creator: Klobukowski, Erik
Partner: UNT Libraries Government Documents Department

Laser ablation-inductively coupled plasma-mass spectrometry: Examinations of the origins of polyatomic ions and advances in the sampling of particulates

Description: This dissertation provides a general introduction to Inductively coupled plasma-mass spectrometry (ICP-MS) and laser ablation (LA) sampling, with an examination of analytical challenges in the employment of this technique. It discusses the origin of metal oxide ions (MO+) in LA-ICP-MS, as well as the effect of introducing helium and nitrogen to the aerosol gas flow on the formation of these polyatomic interferences. It extends the study of polyatomic ions in LA-ICP-MS to metal argide (MAr+) species, an additional source of possible significant interferences in the spectrum. It describes the application of fs-LA-ICP-MS to the determination of uranium isotope ratios in particulate samples.
Date: November 30, 2011
Creator: Witte, Travis
Partner: UNT Libraries Government Documents Department

Transition metal complexes of oxazolinylboranes and cyclopentadienyl-bis(oxazolinyl)borates: Catalysts for asymmetric olefin hydroamination and acceptorless alcohol decarbonylation

Description: The research presented and discussed in this dissertation involves the synthesis of transition metal complexes of oxazolinylboranes and cyclopentadienyl-bis(oxazolinyl)borates, and their application in catalytic enantioselective olefin hydroamination and acceptorless alcohol decarbonylation. Neutral oxazolinylboranes are excellent synthetic intermediates for preparing new borate ligands and also developing organometallic complexes. Achiral and optically active bis(oxazolinyl)phenylboranes are synthesized by reaction of 2-lithio-2-oxazolide and 0.50 equiv of dichlorophenylborane. These bis(oxazolinyl)phenylboranes are oligomeric species in solid state resulting from the coordination of an oxazoline to the boron center of another borane monomer. The treatment of chiral bis(oxazolinyl)phenylboranes with sodium cyclopentadienide provide optically active cyclopentadienyl-bis(oxazolinyl)borates H[PhB(C{sub 5}H{sub 5})(Ox{sup R}){sub 2}] [Ox{sup R} = Ox{sup 4S-iPr,Me2}, Ox{sup 4R-iPr,Me2}, Ox{sup 4S-tBu]}. These optically active proligands react with an equivalent of M(NMe{sub 2}){sub 4} (M = Ti, Zr, Hf) to afford corresponding cyclopentadienyl-bis(oxazolinyl)borato group 4 complexes {PhB(C{sub 5}H{sub 4})(Ox{sup R}){sub 2}}M(NMe{sub 2}){sub 2} in high yields. These group 4 compounds catalyze cyclization of aminoalkenes at room temperature or below, providing pyrrolidine, piperidine, and azepane with enantiomeric excesses up to 99%. Our mechanistic investigations suggest a non-insertive mechanism involving concerted C−N/C−H bond formation in the turnover limiting step of the catalytic cycle. Among cyclopentadienyl-bis(oxazolinyl)borato group 4 catalysts, the zirconium complex {PhB(C{sub 5}H{sub 4})(Ox{sup 4S-iPr,Me2}){sub 2}}Zr(NMe{sub 2}){sub 2} ({S-2}Zr(NMe{sub 2}){sub 2}) displays highest activity and enantioselectivity. Interestingly, {S-2}Zr(NMe{sub 2}){sub 2} also desymmetrizes olefin moieties of achiral non-conjugated aminodienes and aminodiynes during cyclization. The cyclization of aminodienes catalyzed by {S-2}Zr(NMe{sub 2}){sub 2} affords diastereomeric mixture of cis and trans cylic amines with high diasteromeric ratios and excellent enantiomeric excesses. Similarly, the desymmetrization of alkyne moieties in {S-2}Zr(NMe{sub 2}){sub 2}-catalyzed cyclization of aminodiynes provides corresponding cyclic imines bearing quaternary stereocenters with enantiomeric excesses up to 93%. These stereoselective desymmetrization reactions are significantly affected by concentration of the substrate, temperature, and the presence of a ...
Date: December 17, 2012
Creator: Manna, Kuntal
Partner: UNT Libraries Government Documents Department

Rhodium mediated bond activation: from synthesis to catalysis

Description: Recently, our lab has developed monoanionic tridentate ligand, To{sup R}, showing the corresponding coordination chemistry and catalyst reactivity of magnesium, zirconium, zinc and iridium complexes. This thesis details synthetic chemistry, structural study and catalytic reactivity of the To{sup R}-supported rhodium compounds. Tl[To{sup R}] has been proved to be a superior ligand transfer agent for synthesizing rhodium complexes. The salt metathesis route of Tl[To{sup M}] with [Rh({mu}-Cl)(CO)]{sub 2} and [Rh({mu}- Cl)(COE)]{sub 2} gives To{sup M}Rh(CO){sub 2} (2.2) and To{sup M}RhH({eta}{sup 3}-C{sub 8}H{sub 13}) (3.1) respectively while Tl[To{sup P}] with [Rh({mu}-Cl)(CO)]{sub 2} affords To{sup P}Rh(CO){sub 2} (2.3). 2.2 reacts with both strong and weak electrophiles, resulting in the oxazoline N-attacked and the metal center-attacked compounds correspondingly. Using one of the metal center-attacked electrophiles, 2.3 was demonstrated to give high diastereoselectivity. Parallel to COE allylic C-H activation complex 3.1, the propene and allylbenzene allylic C-H activation products have also been synthesized. The subsequent functionalization attempts have been examined by treating with Brønsted acids, Lewis acids, electrophiles, nucleophiles, 1,3-dipolar reagents and reagents containing multiple bonds able to be inserted. Various related complexes have been obtained under these conditions, in which one of the azide insertion compounds reductively eliminates to give an allylic functionalization product stoichiometrically. 3.1 reacts with various primary alcohols to give the decarbonylation dihydride complex To{sup M}Rh(H){sub 2}CO (4.1). 4.1 shows catalytic reactivity for primary alcohol decarbonylation under a photolytic condition. Meanwhile, 2.2 has been found to be more reactive than 4.1 for catalytic alcohol decarbonylation under the same condition. Various complexes and primary alcohols have been investigated as well. The proposed mechanism is based on the stochiometric reactions of the possible metal and organic intermediates. Primary amines, hypothesized to undergo a similar reaction pathway, have been verified to give dehydrogenative coupling product, imines. In the end, the well-developed neutral tridentate Tpm ...
Date: March 6, 2012
Creator: Ho, Hung-An
Partner: UNT Libraries Government Documents Department

United abominations: Density functional studies of heavy metal chemistry

Description: Carbonyl and nitrile addition to uranyl (UO{sup 2}{sup 2+}) are studied. The competition between nitrile and water ligands in the formation of uranyl complexes is investigated. The possibility of hypercoordinated uranyl with acetone ligands is examined. Uranyl is studied with diactone alcohol ligands as a means to explain the apparent hypercoordinated uranyl. A discussion of the formation of mesityl oxide ligands is also included. A joint theory/experimental study of reactions of zwitterionic boratoiridium(I) complexes with oxazoline-based scorpionate ligands is reported. A computational study was done of the catalytic hydroamination/cyclization of aminoalkenes with zirconium-based catalysts. Techniques are surveyed for programming for graphical processing units (GPUs) using Fortran.
Date: April 2, 2012
Creator: Schoendorff, George
Partner: UNT Libraries Government Documents Department

A GENERAL THEORY OF THE SPECTROSCOPIC PROPERTIES OF PARTIALLY ORDERED ENSEMBLES. II. TWO-VECTOR PROBLEMS

Description: We have expanded on the results of an earlier paper [J. Chem. Phys. 72, 221 (1980)] which deals with a method for determining the response of a static, partially ordered ensemble of molecules to various types of electromagnetic probes. In this paper we consider types of spectroscopy whose response depends on the location of two vectors in an axis system fixed with respect to the molecule. Examples of such spectroscopies discussed in detail include fluorescence polarization, photoselection linear dichroism, Raman spectroscopy and two-photon absorption. We outline the kinds of structural information available from polarization experiments on partially ordered ensembles.
Date: April 1, 1980
Creator: Nairn, John A.; Friesner, R. & Sauer, Kenneth
Partner: UNT Libraries Government Documents Department

Uranyl Sequestration: Synthesis and Structural Characterization of Uranyl Complexes with a Tetradentate Methylterephthalamide Ligand

Description: Uranyl complexes of a bis(methylterephthalamide) ligand (LH{sub 4}) have been synthesized and characterized by X-ray crystallography. The structure is an unexpected [Me{sub 4}N]{sub 8}[L(UO{sub 2})]{sub 4} tetramer, formed via coordination of the two MeTAM units of L to two uranyl moieties. Addition of KOH to the tetramer gave the corresponding monomeric uranyl methoxide species [Me{sub 4}N]K{sub 2}[LUO{sub 2}(OMe)].
Date: March 7, 2011
Creator: Ni, Chengbao; Shuh, David & Raymond, Kenneth
Partner: UNT Libraries Government Documents Department

Charge Transfer and Support Effects in Heterogeneous Catalysis

Description: The kinetic, electronic and spectroscopic properties of two‐dimensional oxide‐supported catalysts were investigated in order to understand the role of charge transfer in catalysis. Pt/TiO{sub 2} nanodiodes were fabricated and used as catalysts for hydrogen oxidation. During the reaction, the current through the diode, as well as its I‐V curve, were monitored, while gas chromatography was used to measure the reaction rate. The current and the turnover rate were found to have the same temperature dependence, indicating that hydrogen oxidation leads to the non‐adiabatic excitation of electrons in Pt. A fraction of these electrons have enough energy to ballistically transport through Pt and overcome the Schottky barrier at the interface with TiO{sub 2}. The yield for this phenomenon is on the order of 10{sup ‐4} electrons per product molecule formed, similar to what has been observed for CO oxidation and for the adsorption of many different molecules. The same Pt/TiO{sub 2} system was used to compare currents in hydrogen oxidation and deuterium oxidation. The current through the diode under deuterium oxidation was found to be greater than under hydrogen oxidation by a factor of three. Weighted by the difference in turnover frequencies for the two isotopes, this would imply a chemicurrent yield 5 times greater for D{sub 2} compared to H{sub 2}, contrary to what is expected given the higher mass of D{sub 2}. Reversible changes in the rectification factor of the diode are observed when switching between D{sub 2} and H{sub 2}. These changes are a likely cause for the differences in current between the two isotopes. In the nanodiode experiments, surface chemistry leads to charge flow, suggesting the possibility of creating charge flow to tune surface chemistry. This was done first by exposing a Pt/Si diode to visible light while using it as a catalyst for H{sub 2} oxidation. ...
Date: December 21, 2011
Creator: Hervier, Antoine
Partner: UNT Libraries Government Documents Department

Syntheses, Structure, Magnetism, and Optical Properties of the Ordered Interlanthanide Copper Chalcogenides Ln{sub 2}YbCuQ{sub 5} (Ln = La, Ce, Pr, Nd, Sm; Q = S, Se): Evidence for Unusual Magnetic Ordering in Sm{sub 2}YbCuS{sub 5}

Description: Ln{sub 2}YbCuQ{sub 5} (Ln = La, Ce, Pr, Nd, Sm; Q = S, Se) have been prepared by direct reaction of the elements in Sb{sub 2}Q{sub 3} (Q = S, Se) fluxes at 900 °C. All compounds have been characterized by single-crystal X-ray diffraction methods and they are isotypic. The structure of Ln{sub 2}YbCuQ{sub 5} consists of one-dimensional {sup 1}{sub {infinity}} [YbCuQ{sub 5}]{sup 6-} ribbons extending along the b axis that are connected by larger Ln{sup 3+} ions. Each ribbon is constructed from two single chains of [YbQ{sub 6}] octahedra with one double chain of [CuQ{sub 5}] trigonal bipyramids in the middle. All three chains connect with each other via edge-sharing. There are two crystallographically unique Ln atoms, one octahedral Yb site, and two disordered Cu positions inside of distorted Q{sub 5} trigonal bipyramids. Both Ln atoms are surrounded by eight Q atoms in bicapped trigonal prisms. The magnetic properties of Ln{sub 2}YbCuQ{sub 5} have been characterized using magnetic susceptibility and heat capacity measurements, while their optical properties have been explored using UV-vis-NIR diffuse reflectance spectroscopy. Cesub 2}YbCuSe{sub 5}, La{sub 2}YbCuS{sub 5}, Ce{sub 2}YbCuS{sub 5}, and Pr{sub 2}YbCuS{sub 5} are Curie-Weiss paramagnets. La{sub 2}YbCuSe{sub 5} and Nd{sub 2}YbCuS{sub 5} show evidence for short-range antiferromagnetic ordering at low temperatures. Sm{sub 2}YbCuS{sub 5} shows magnetic ordering at 5.9 K, followed by negative magnetization at low external fields. The band gaps of La{sub 2}YbCuSe{sub 5}, Ce{sub 2}YbCuSe{sub 5}, La{sub 2}YbCuS{sub 5}, Ce{sub 2}YbCuS{sub 5}, Pr{sub 2}YbCuS{sub 5}, Nd{sub 2}YbCuS{sub 5},and Sm{sub 2}YbCuS{sub 5} are 1.15 eV, 1.05 eV, 1.45 eV, 1.37 eV, 1.25 eV, 1.35 eV, and 1.28 eV respectively.
Date: November 19, 2010
Creator: Jin, Geng Bang; Choi, Eun Sang; Guertin, Robert P.; Booth, Corwin H. & Albrecht-Schmitt, Thomas E.
Partner: UNT Libraries Government Documents Department

THE ACTIVITY COEFFICIENT OF AQUEOUS NaHCO{sup 3}

Description: The determination of the activity coefficient and related properties of sodium bicarbonate presents special problems because of the appreciable vapor pressure of CO{sub 2} above such solutions. With the development of reliable equations for the thermodynamic properties of mixed electrolytes, it is possible to determine the parameters for NaHCO{sub 3} from cell measurements or NaCl-NaHCO{sub 3} mixtures. Literature data are analyzed to illustrate the method and provide interim values, but it is noted that further measurements over a wider range of concentrations would yield more definitive results. An estimate is also given for the activity coefficient of KHCO{sub 3}.
Date: December 1, 1979
Creator: Pitzer, Kenneth S. & Peiper, J. Christopher
Partner: UNT Libraries Government Documents Department

CORRELATION BETWEEN THE OPTICAL AND MAGNETIC PROPERTIES OF FERRIC N-ACETYLATED HEME OCTAPEPTIDE COMPLEXES

Description: The room temperature magnetic susceptibility of the complexes of the ferric N-acetylated heme octapeptide (N-H8PT) from horse heart cytochrome c is known to be generally consistent with the absorption and magnetic circular dichroism (MCD) spectra of these complexes. However, the N-acetylated methionine complex of the N-H8PT, which has axial coordination identical to that of the parent molecule, is found to exhibit a thermal mixture of high spin (S=5/2) and low spin (S=1/2) states. The temperature dependence of the magnetic susceptibility of the N-acetylmethionine complex yields {Delta}H{sup 0} = -7.6kca1/mole and {Delta}S° = -25.9 e.u. for a high to low spin transition. The electron spin resonance (ESR) spectrum of the N-acetylmethionine complex indicates a low spin ground state, with g values at 1.51, 2.31, and 2.91, which are distinct from those of cytochrome c. The axial ({Delta}) and rhombic (V) distortion parameters of the {sup 2}T{sub 2g} state correspond to 2.96{lambda} and 1.94{lambda}, respectively, where {lambda} is the spin-orbit coupling constant. A model is proposed to account for the uniqueness of the N-acetylmethionine complex: a change in the Fe-S distance may play a role in regulating the redox properties of cytochrome c.
Date: May 1, 1980
Creator: Yang, E.K. & Sauer, K.
Partner: UNT Libraries Government Documents Department

CYCLOPETIDE ALKALOIDS. SYNTHETIC, SPECTROSCOPIC AND CONFORMATIONAL STUDIES OF PHENCYCLOPEPTINE MODEL COMPOUNDS

Description: Peptide cyclization via the p-nitrophenyl ester of 4-methyl-3-[4'-{beta}-N-(N'-tert-butyloxycarbonyl-L~prolyl)-aminoethyl]phenoxy-pentanoic acid (9) has afforded a single cyclopeptide diastereomer,9R-isopropyl-5S,6-trimethylene-8-dearnino-1,2-dihydro-p-phencyclopeptine (4), in 36% yield. From the comparative analysis of the UV, IR, CD, and {sup 1}H NMR spectra of 4 and cyclopeptide 5S,6-trimethylene 8-deamino-1,2-dihydro-p-phencyclopeptine (3d), of known geometry, the conformational identities of the 14-membered ring systems were ascertained. From these data the assignment of R stereochemistry at C9 for cyclopeptide 4 was deduced. Since the stereochemistry at C9 in the naturally occurring phencyclopeptines is the same, these results suggest a feasible route to the stereoselective total synthesis of the phencyclopeptines.
Date: May 1, 1980
Creator: Goff, Dane; Lagarias, J. Clark; Shih, Willy C.; Klein, Melvin P. & Rapoport, Henry
Partner: UNT Libraries Government Documents Department

REACTIONS OF {eta}{sup 5}-CYCLOPENTADIENYLCOBALT(III) ALKYLS WITH COBALT(I) PHOSPHINES AND IRON CARBONYLS. EVIDENCE FOR DIRECT {eta}{sup 5} -CYCLOPENTADIENYL AND TRIMETHYLPHOSPHINE GROUP TRANSFER BETWEEN METAL CENTERS

Description: We have found that {eta}{sup 5}-methylcyclopentadienyl- (triphenylphosphine)dimethylcobalt(III) (1) undergoes intermolecular cyclopentadienyl ligand exchange with {eta}{sup 5}-cyclopentadienylbistriphenylphosphinecobalt(I). The unsubstituted cyclopentadienyl(triphenylphosphine)dimethylco-balt(III) undergoes exchange of phosphine for carbon monoxide with both Fe(CO){sub 4} and Fe(CO){sub 5} by two different mechanisms. The first involves electrophilic displacement of coordinated phosphine by unsaturated Fe(CO){sub 4} and the second takes place by electrophilic displacement of CO from Fe(CO){sub 5} by the unsaturated CpCoMe{sub 2} fragment (generated by phosphine dissociation from the saturated starting material).
Date: August 1, 1980
Creator: Bryndza, H.E. & Bergman, R.G.
Partner: UNT Libraries Government Documents Department

PHYSICAL ORGANIC STUDIES OF ORGANOMETALLIC REACTIONS

Description: The mechanisms of reactions of organotransition metal complexes have only begun to be understood in detail during the last ten years. The complementary interaction of techniques and concepts developed earlier in studies of organic reaction mechanisms, with those commonly used in inorganic chetnistry, has played a crucial role in helping to elucidate organor.1etall.ic reaction mechanisms. A few systems in which this interaction has proved especially fruitful are discussed in this article.
Date: September 1, 1980
Creator: Bergman, Robert G.
Partner: UNT Libraries Government Documents Department

SEPARATION OF DIASTEREOMERS, STRUCTURAL ISOMERS, AND HOMOLOGS OF n5 -CYCLOPENTADIENYL COBALT AND DINUCLEAR MOLYBDENUM COMPLEXES BY REVERSE PHASE HIGH PERFORMANCE LIQUID CHROMATOGRAPHY USING DEOXYGENATED SOLVENTS

Description: High Performance Liquid Chromatography (HPLC) is being used as an analytical and preparative tool for the characterization and isolation of a series of air-sensitive organometallic compounds, Reverse phase chranatography with octadecylsilyl-modified silica (ODS) as a stationary phase and polar mobile phases saturated with argon are employed in the separation of products,
Date: November 1, 1980
Creator: Huggins, John M.; King, Jr., Joseph A.; Peter, K.; Vollhardt, C. & Winter, Mark J.
Partner: UNT Libraries Government Documents Department

OPTICAL PROPERTIES OF MOLECULES CHEMISORBED ON THE Ni(111) SURFACE

Description: The adsorption of a variety of molecules on Ni(111) is studied UV/visible spectroscopic ellipsometry. The spectra were analyzed within a simple dielectric model. The absorption spectra of annealed, thin, condensed layers of pyrazine, pyridine, and naphthalene on the Ni(111) surface resemble bulk crystal spectra, indicating minimal perturbations due to the metal substrate. Chemisorption of molecules on the Ni(111) surface produced enhanced absorption between 2800{Angstrom} and 3100{Angstrom}. The wide range of adsorbate properties and surface chemistry suggest a modification of the optical response of the metal upon chemisorption. This enhanced optical absorption is attributed to nonvertical interband transitions made possible by loss of translational invariance at the surface.
Date: February 1, 1981
Creator: Harris, C.B.; Robota, H.J. & Whitmore, P.M.
Partner: UNT Libraries Government Documents Department

OPTICAL PROPERTIES OF MOLECULES CHEMISORBED ON THE Ni(111) SURFACE

Description: The adsorption of a series of molecules on Ni(111) is studied by UV/visible spectroscopic ellipsometry. The spectra were analyzed within a simple dielectric model. Chemisorption of molecules on the Ni(111) surface produces a peak in the overlayer optical response at 4.2 eV. This absorption peak is attributed to the selective enhancement of bulk interband excitations resulting from perturbations of the metal orbitals upon chemisorption.
Date: August 1, 1981
Creator: Robota, H.J.; Whitmore, P.M.; Harris, C.B. & q
Partner: UNT Libraries Government Documents Department