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Creation and destruction of C{sub 60} and other fullerene solids. Final report

Description: The 1990 announcement of the Huffman-Kratschmer fullerene-production technique set off a world-wide explosion of research into the properties and potential applications of C{sub 60} and C{sub 70}. In the last five years, 4,000+ fullerene articles have appeared in the scientific literature dealing with these fascinating molecules and their condensed phases. They possess a complex chemistry reminiscent of the alkenes, and this has led to the syntheses of numerous new compounds and fullerene-based materials, with suggested applications ranging from medicine to photo-conducting polymers to rocket fuel. The work summarized in this report focused on the creation and destruction of fullerene-based materials, for the purpose of producing new materials of interest. This three year project was supported by a grant from the Advanced Energy Projects Division, Office of Basic Energy Sciences, U.S. Department of Energy (DE-FG03-93ER12133). Following are outlines of the work completed in each of the three years, a section devoted to the professional and educational development of those involved, a brief section on the outlook for fullerene-based materials, and an appendix listing the publications resulting from this project.
Date: June 5, 1996
Creator: Huffman, D. R.
Partner: UNT Libraries Government Documents Department

2011 Organometallic Chemistry (July 10-15, 2011, Salve Regina University, Newport, RI)

Description: Organometallic chemistry has played and will continue to play a significant role in helping us understand the way bonds are made or broken in the presence of a transition metal complex. Current challenges range from the efficient exploitation of energy resources to the creative use of natural and artificial enzymes. Most of the new advances in the area are due to our extended understanding of processes at a molecular level due to new mechanistic studies, techniques to detect reaction intermediates and theory. The conference will bring the most recent advances in the field including nanocatalysis, surface organometallic chemistry, characterization techniques, new chemical reactivity and theoretical approaches along with applications to organic synthesis and the discovery of new materials. The Conference will bring together a collection of investigators who are at the forefront of their field, and will provide opportunities for junior scientists and graduate students to present their work in poster format and exchange ideas with leaders in the field. Six outstanding posters will be selected for short talks. The collegial atmosphere of this Conference, with programmed discussion sessions as well as opportunities for informal gatherings in the afternoons and evenings, provides an avenue for scientists from different disciplines to brainstorm and promotes cross-disciplinary collaborations in the various research areas represented. Graduate students and postdoctoral fellows should also consider participating in the Gordon Research Seminar on Organometallic Chemistry (July 9-10, same location) which is specially designed to promote interaction and discussion between junior scientists.
Date: July 15, 2011
Creator: Bunel, Dr. Emilio
Partner: UNT Libraries Government Documents Department

Early Unstable CO2-Fixation Products in Photosynthesis

Description: Some chemical, physical, and chromatographic properties of the hydroxylamine stabilized early products of CO{sub 2} fixation in photosynthesis are described. Although no definitive structural information is yet available, these properties, together with the biochemical context in which the material appears, make possible some likely suggestions about the nature of the substances.
Date: December 19, 1957
Creator: Metzner, Helmut; Metzner, Barbara & Calvin, Melvin
Partner: UNT Libraries Government Documents Department

Path of Carbon in Photosynthesis III

Description: Although the overall reaction of photosynthesis can be specified with some degree of certainty (CO{sub 2} + H{sub 2}O + light {yields} sugars + possibly other reduced substances), the intermediates through which the carbon passes during the course of this reduction have, until now, been largely a matter of conjecture. The availability of isotopic carbon, that is, a method of labeling the carbon dioxide, provides the possibility of some very direct experiments designed to recognize these intermediates and, perhaps, help to understand the complex sequence and interplay of reactions which must constitute the photochemical process itself. The general design of such experiments is an obvious one, namely the exposure of the green plant to radioactive carbon dioxide and light under a variety of conditions and for continually decreasing lengths of time, followed by the identification of the compounds into which the radioactive carbon is incorporated under each condition and time period. From such data it is clear that in principle, at least, it should be possible to establish the sequence of compounds in time through which the carbon passes on its path from carbon dioxide to the final products. In the course of shortening the photosynthetic times, one times, one ultimately arrives at the condition of exposing the plants to the radioactive carbon dioxide with a zero illumination time, that is, in the dark. Actually, in the work the systematic order of events was reversed, and they have begun by studying first the dark fixation and then the shorter photosynthetic times. The results of the beginnings of this sort of a systematic investigation are given in Table I which includes three sets of experiments, namely a dark fixation experiment and two photosynthetic experiments, one of 30 seconds duration and the other of 60 seconds duration.
Date: June 1, 1948
Creator: Benson, A.A. & Calvin, M.
Partner: UNT Libraries Government Documents Department

The Relationship Between the Metabolic Pools of Photosynthetic andRespiratory Intermediates

Description: Using radioactive carbon dioxide, an attempt has been made to distinguish the various pools of intermediary metabolism which may be physically or chemically separate within the cell. Some correlation between the structural elements of the cells and these pools appears possible.
Date: July 1, 1958
Creator: Moses, V.; Calvin, M.; Holm-Hansen, O. & Bassham, J.A.
Partner: UNT Libraries Government Documents Department

THE PATH OF CARBON IN PHOTOSYNTHESIS. X. CARBON DIOXIDEASSIMILATION IN PLANTS

Description: The conclusions which have been drawn from the results of C{sup 14}O{sub 2} fixation experiments with a variety of plants are developed in this paper. The evidence for thermochemical reduction of carbon dioxide fixation intermediates is presented and the results are interpreted from such a viewpoint.
Date: April 1, 1950
Creator: Calvin, M.; Bassham, J .A.; Benson, A.A.; Lynch, V.; Ouellet, C.; Schou, L. et al.
Partner: UNT Libraries Government Documents Department

Molecular Components of Catalytic Selectivity

Description: Selectivity, that is, to produce one molecule out of many other thermodynamically feasible product molecules, is the key concept to develop 'clean manufacturing' processes that do not produce byproducts (green chemistry). Small differences in potential energy barriers for elementary reaction steps control which reaction channel is more likely to yield the desired product molecule (selectivity), instead of the overall activation energy for the reaction that controls turnover rates (activity). Recent studies have demonstrated the atomic- or molecular-level tailoring of parameters such as the surface structures of active sites that give rise to nanoparticle size and shape dependence of turnover rates and reaction selectivities. Here, we highlight seven molecular components that influence reaction selectivities. These include: surface structure, adsorbate-induced restructuring, adsorbate mobility, reaction intermediates, surface composition, charge transport, and oxidation states for model metal single crystal and colloid nanoparticle catalysts. We show examples of their functioning and describe in-situ instruments that permit us to investigate their roles in surface reactions.
Date: July 2, 2008
Creator: Somorjai, Gabor A. & Park, Jeong Y.
Partner: UNT Libraries Government Documents Department

Gas-Phase Molecular Dynamics: High Resolution Spectroscopy and Collision Dynamics of Transient Species

Description: This research is carried out as part of the Gas-Phase Molecular Dynamics program in the Chemistry Department at Brookhaven National Laboratory. High-resolution spectroscopy, augmented by theoretical and computational methods, is used to investigate the structure and collision dynamics of chemical intermediates in the elementary gas-phase reactions involved in combustion chemistry. Applications and methods development are equally important experimental components of this work.
Date: April 3, 2009
Creator: Hall,G.E. & Sears, T.J.
Partner: UNT Libraries Government Documents Department

Hydrogenation of the alpha,beta-Unsaturated Aldehydes Acrolein, Crotonaldehyde, and Prenal over Pt Single Crystals: A Kinetic and Sum-Frequency Generation Vibrational Spectroscopy Study

Description: Sum-frequency generation vibrational spectroscopy (SFG-VS) and kinetic measurements using gas chromatography have been used to study the surface reaction intermediates during the hydrogenation of three {alpha},{beta}-unsaturated aldehydes, acrolein, crotonaldehyde, and prenal, over Pt(111) at Torr pressures (1 Torr aldehyde, 100 Torr hydrogen) in the temperature range of 295K to 415K. SFG-VS data showed that acrolein has mixed adsorption species of {eta}{sub 2}-di-{sigma}(CC)-trans, {eta}{sub 2}-di-{sigma}(CC)-cis as well as highly coordinated {eta}{sub 3} or {eta}{sub 4} species. Crotonaldehyde adsorbed to Pt(111) as {eta}{sub 2} surface intermediates. SFG-VS during prenal hydrogenation also suggested the presence of the {eta}{sub 2} adsorption species, and became more highly coordinated as the temperature was raised to 415K, in agreement with its enhanced C=O hydrogenation. The effect of catalyst surface structure was clarified by carrying out the hydrogenation of crotonaldehyde over both Pt(111) and Pt(100) single crystals while acquiring the SFG-VS spectra in situ. Both the kinetics and SFG-VS showed little structure sensitivity. Pt(100) generated more decarbonylation 'cracking' product while Pt(111) had a higher selectivity for the formation of the desired unsaturated alcohol, crotylalcohol.
Date: November 26, 2008
Creator: Kliewer, C.J. & Somorjai, G.A.
Partner: UNT Libraries Government Documents Department

Sum Frequency Generation Vibrational Spectroscopy of Pyridine Hydrogenation on Platinum Nanoparticles

Description: Pyridine hydrogenation in the presence of a surface monolayer consisting of cubic Pt nanoparticles stabilized by tetradecyltrimethylammonium bromide (TTAB) was investigated by sum frequency generation (SFG) vibrational spectroscopy using total internal reflection (TIR) geometry. TIR-SFG spectra analysis revealed that a pyridinium cation (C{sub 5}H{sub 5}NH{sup +}) forms during pyridine hydrogenation on the Pt nanoparticle surface, and the NH group in the C{sub 5}H{sub 5}NH{sup +} cation becomes more hydrogen bound with the increase of the temperature. In addition, the surface coverage of the cation decreases with the increase of the temperature. An important contribution of this study is the in situ identification of reaction intermediates adsorbed on the Pt nanoparticle monolayer during pyridine hydrogenation.
Date: February 22, 2008
Creator: Bratlie, Kaitlin M.; Komvopoulos, Kyriakos & Somorjai, Gabor A.
Partner: UNT Libraries Government Documents Department

Reaction Selectivity in Heterogeneous Catalysis

Description: The understanding of selectivity in heterogeneous catalysis is of paramount importance to our society today. In this review we outline the current state of the art in research on selectivity in heterogeneous catalysis. Current in-situ surface science techniques have revealed several important features of catalytic selectivity. Sum frequency generation vibrational spectroscopy has shown us the importance of understanding the reaction intermediates and mechanism of a heterogeneous reaction, and can readily yield information as to the effect of temperature, pressure, catalyst geometry, surface promoters, and catalyst composition on the reaction mechanism. DFT calculations are quickly approaching the ability to assist in the interpretation of observed surface spectra, thereby making surface spectroscopy an even more powerful tool. HP-STM has revealed three vitally important parameters in heterogeneous selectivity: adsorbate mobility, catalyst mobility, and selective site-blocking. The development of size controlled nanoparticles from 0.8 to 10 nm, of controlled shape, and of controlled bimetallic composition has revealed several important variables for catalytic selectivity. Lastly, DFT calculations may be paving the way to guiding the composition choice for multi-metallic heterogeneous catalysis for the intelligent design of catalysts incorporating the many factors of selectivity we have learned.
Date: February 2, 2009
Creator: Somorjai, Gabor A. & Kliewer, Christopher J.
Partner: UNT Libraries Government Documents Department

Modeling DNA Replication Intermediates

Description: While there is now available a great deal of information on double stranded DNA from X-ray crystallography, high resolution NMR and computer modeling, very little is known about structures that are representative of the DNA core of replication intermediates. DNA replication occurs at a single strand/double strand junction and bulged out intermediates near the junction can lead to frameshift mutations. The single stranded domains are particularly challenging. Our interest is focused on strategies for modeling the DNA of these types of replication intermediates. Modeling such structures presents special problems in addressing the multiple minimum problem and in treating the electrostatic component of the force field. We are testing a number of search strategies for locating low energy structures of these types and we are also investigating two different distance dependent dielectric functions in the coulombic term of the force field. We are studying both unmodified DNA and DNA damaged by aromatic amines, carcinogens present in the environment in tobacco smoke, barbecued meats and automobile exhaust. The nature of the structure adopted by the carcinogen modified DNA at the replication fork plays a key role in determining whether the carcinogen will cause a mutation during replication that can initiate the carcinogenic process. In the present work results are presented for unmodified DNA.
Date: June 1, 1997
Creator: Broyde, S.; Roy, D. & Shapiro, R.
Partner: UNT Libraries Government Documents Department

Molecular structure determination for photogenerated intermediates in photoinduced electron transfer reactions using steady-state and transient XAFS

Description: Many photoinduced electron transfer reactions are accompanied by nuclear rearrangements of the molecules involved. In order to understand the reactivities of the molecules and the reaction mechanisms, precise information on the molecular structural changes accompanying the electron transfer is often required. We present here conventional XAFS and transient energy dispersive XAFS studies on structures of excited and photoinduced charge separated state of porphyrin and porphyrin based supermolecules, and structures of TiO{sub 2} colloid and the heavymetal ions that bind to the colloid surfaces during photocatalytic reductions.
Date: October 1, 1996
Creator: Chen, L.X.; Wasielewski, M.R. & Rajh, T.
Partner: UNT Libraries Government Documents Department

Excess Sodium Tetraphenylborate and Intermediates Decomposition Studies

Description: The stability of excess amounts of sodium tetraphenylborate (NaTPB) in the In-Tank Precipitation (ITP) facility depends on a number of variables. Concentration of palladium, initial benzene, and sodium ion as well as temperature provide the best opportunities for controlling the decomposition rate. This study examined the influence of these four variable on the reactivity of palladium-catalyzed sodium tetraphenylborate decomposition. Also, single effects tests investigated the reactivity of simulants with continuous stirring and nitrogen ventilation, with very high benzene concentrations, under washed sodium concentrations, with very high palladium concentrations, and with minimal quantities of excess NaTPB.
Date: December 7, 1998
Creator: Barnes, M.J.
Partner: UNT Libraries Government Documents Department

Study of intermediates from transition metal excited-state electron-transfer reactions. Final report, August 4, 1986--August 31, 1997

Description: The techniques of continuous photolysis and pulsed laser flash photolysis, continuous and pulse radiolysis, fast-scan cyclic voltammetry, and time-resolved fluorimetry have been used to examine intramolecular electron transfer within the solvent quenching cage, photodynamics of quenching of the excited states of transition-metal photosensitizers, the properties of excites states and one-electron reduced forms, ground- and excited-state interactions with solutes, and photoinduced oxidations of organic solutes in aqueous solution. The following specific areas were examined: (1) the parameters that govern the yields of redox products from excited-state electron-transfer quenching reactions; (2) the mediation of the properties of excited states and one-electron reduced forms by the ligands and the solution medium; (3) the effect of the interactions between the ground state of the complex and the solution components on the behavior of the excited state; (4) the yields of singlet oxygen from excited-state energy-transfer quenching by O{sub 2}; and (5) the oxidations of solutes by singlet oxygen, excited-state electron-transfer quenching, and free radicals. This report contains the abstracts of 50 publications describing the studies.
Date: December 31, 1997
Creator: Hoffman, M.Z.
Partner: UNT Libraries Government Documents Department

Fundamental studies of reactive intermediates in homogeneous catalysis. Final technical report

Description: The chief aims during the contract period were to design, construct and implement a new flowing afterglow-guided ion beam instrument for use in determining thermochemical properties of organometallic species pertinent to homogeneous catalysis, and to develop an electrospray ionization (ESI) source for the flowing afterglow-triple quadrupole apparatus for use in real-time analysis of reactive intermediates in catalytically active solutions. Both goals were achieved. In parallel with development of the guided ion beam and electrospray ionization experiments, the author used existing equipment to work on some of the problems outlined in the previous proposal, and to open up new research areas. A summary of research activities and publications acknowledging DOE support follows.
Date: September 1, 1998
Partner: UNT Libraries Government Documents Department

On the kinetics of high temperature oxidation of copper foils : a quantitative in situ QEXAFS investigation.

Description: Based on previous results [1] further details of the oxidation of copper foil 2 Cu + O{sub 2} {r_arrow} 2 CuO were resolved using high quality, high temperature Cu{sub 2}O and CuO standards for Cu-K XAFS and Cu-K PCA [2] analysis. These were prepared from copper foils using the same experimental techniques as for the oxidation under study. As the reaction can be divided into a step-wise oxidation mechanism: 2 Cu + 0.5 O{sub 2} {r_arrow}Cu{sub 2}O; Cu{sub 2}O + 0.5 O{sub 2} {r_arrow} 2 CuO, we attempted to check whether the formation of CuO is kinetically inhibited (delayed) or whether it takes place simultaneously to the formation of Cu{sub 2}O. To achieve an optimal time resolution the QEXAFS technique [3] was applied. This investigation was completed by XRD and SEM investigations on samples quenched within the oxidation period.
Date: March 5, 1998
Creator: Hilbrandt, N.
Partner: UNT Libraries Government Documents Department

Pyrrole Hydrogenation over Rh(111) and Pt(111) Single-Crystal Surfaces and Hydrogenation Promotion Mediated by 1-Methylpyrrole: A Kinetic and Sum-Frequency Generation Vibrational Spectroscopy Study

Description: Sum-frequency generation (SFG) surface vibrational spectroscopy and kinetic measurements using gas chromatography have been used to study the adsorption and hydrogenation of pyrrole over both Pt(111) and Rh(111) single-crystal surfaces at Torr pressures (3 Torr pyrrole, 30 Torr H{sub 2}) to form pyrrolidine and the minor product butylamine. Over Pt(111) at 298 K it was found that pyrrole adsorbs in an upright geometry cleaving the N-H bond to bind through the nitrogen evidenced by SFG data. Over Rh(111) at 298 K pyrrole adsorbs in a tilted geometry relative to the surface through the p-aromatic system. A pyrroline surface reaction intermediate, which was not detected in the gas phase, was seen by SFG during the hydrogenation over both surfaces. Significant enhancement of the reaction rate was achieved over both metal surfaces by adsorbing 1-methylpyrrole before reaction. SFG vibrational spectroscopic results indicate that reaction promotion is achieved by weakening the bonding between the N-containing products and the metal surface because of lateral interactions on the surface between 1-methylpyrrole and the reaction species, reducing the desorption energy of the products. It was found that the ring-opening product butylamine was a reaction poison over both surfaces, but this effect can be minimized by treating the catalyst surfaces with 1-methylpyrrole before reaction. The reaction rate was not enhanced with elevated temperatures, and SFG suggests desorption of pyrrole at elevated temperatures.
Date: March 4, 2008
Creator: Kliewer, Christopher J.; Bieri, Marco & Somorjai, Gabor A.
Partner: UNT Libraries Government Documents Department

Magnetic resonance and optical spectroscopic studies of carotenoids. Progress report, December 1, 1994--November 30, 1995

Description: The fundamental goals of this project are (1) to understand the role of a host matrix in the formation and decay mechanisms of carotenoid cation radical and dication and (2) to determine the special properties of carotenoids that enable them to serve as photoprotective agents in photosynthesis and as possible components in electron transfer processes. Results to date are discussed briefly. Work will continue as outlined in the original proposal with emphasis on using simultaneous electrochemistry EPR, and optical methods, variable temperature electrochemistry using microelectrodes and fast scans to examine the more unstable intermediates formed upon electrochemical oxidation of synthetically prepared carotenoids.
Date: June 1, 1995
Creator: Kispert, L.D.
Partner: UNT Libraries Government Documents Department

Short contact time direct coal liquefaction using a novel batch reactor. Quarterly report, 1996

Description: The objective of this research is to optimize the design and operation of the bench scale batch reactor (SCTBR) for coal liquefaction at short contact times (0.01 to 10 minutes or longer). Additional objectives are to study the kinetics of direct coal liquefaction particularly at short reaction times, and to investigate the role of the organic oxygen components of coal and their reaction pathways during liquefaction. Many of those objectives have already been achieved and others are still in progress. This quarterly report covers further progress toward those objectives. Much of the previous quarterly report was concerned mainly in the retrograde reactions occurring during the liquefaction process. This report is largely devoted to the kinetics and mechanisms of the liquefaction process itself and the influence of the liquefaction solvents.
Date: May 1, 1996
Creator: Klein, M.T.; Calkins, W.H. & Huang, H.
Partner: UNT Libraries Government Documents Department

Supercritical catalysts of light hydrocarbon conversion. DOE PETC eighth quartery report, July 1, 1995--September 30, 1995

Description: The solid superacid catalysts investigated in this project catalyze hydrocarbon conversions by routes involving carbocation intermediates. This report is a summary of mechanisms of hydrocarbon conversion catalyzed by these and related solid acids. This mechanistic information summarized here is important to the present project because it provides guidance for the modeling of the kinetics of the catalytic butane conversion and propane conversion. Because of the difficulty of determining surface reaction intermediates, understanding of surface reaction mechanisms lags far behind that of solution reaction mechanisms, and what is known about the former is fragmentary and often largely based on presumed analogies with the latter, combined with results such as those from tracer experiments, kinetics experiments, and theoretical chemistry.
Date: June 1, 1996
Creator: Gates, B.C.
Partner: UNT Libraries Government Documents Department

The preparation and characterization of linear and cross-linked poly(fluorenyl)

Description: Retrogressive reactions in coal processing are that class of reactions that lead to the formation of high molecular weight materials that are more intractable than those present in the coal prior to processing. This outcome almost always is regarded as deleterious. The present work focuses on the characterization of the acid-catalyzed polymerization of benzylic fluorides, and in particular the synthesis of poly(fluorenyl), as an example of the type of chemistry that may occur in the cross-linked organic matrix of coals when in contact with strong acids. Solution and solid state {sup 13}C NMR spectroscopy was used to characterize the soluble and insoluble polymers. The change in the value of the fraction of aromatic carbon that is protonated is the criterion used to monitor the extent of cross-linking in these polymer preparations. Benzylic fluorides are sensitive substances, prone to further reaction via acid catalyzed heterolytic scission of the C-F bond. The electron deficient reactive intermediate formed in this reaction undergoes electrophilic aromatic substitution. This reaction can be started with catalytic traces of acid and is self-sustaining as HF is generated in equivalent concentrations as the reaction proceeds. The relevance of this naturally non-occurring functional group in coal processing stems from the similar reaction pathway followed by both benzylic fluorides and benzylic alcohols. In the coal matrix, the operation of two exogenous processes--air oxidation and strong acid treatment of the coal (demineralization) creates a situation in which the polymerization discussed herein may occur in the coal. In addition to the polymerization reactions that produce poly(fluorenyl), the subsequent cross-linking of the linear polymer is also reported. In subsequent work, similar chemistry will be applied to soluble lignin as a model more similar to low rank coals.
Date: March 1, 1997
Creator: Hagaman, E.W. & Lee, S.K.
Partner: UNT Libraries Government Documents Department

Pulse radiolytic studies of electron transfer processes and applications to solar photochemistry. Progress report

Description: The pulse radiolysis technique is applied to the study of electron transfer processes in a variety of chemical systems. Reactive intermediates are produced in solution by electron pulse irradiation and the kinetics of their reactions are followed by time resolved absorption spectrophotometry. Complementary experiments are carried out with excimer laser flash photolysis. These studies are concerned with mechanisms, kinetics, and thermodynamics of reactions of organic and inorganic radicals and unstable oxidation states of metal ions. Reactions are studied in both aqueous and non-aqueous solutions. The studies focus on the unique ability of pulse radiolysis to provide absolute rate constants for reactions of many inorganic radicals and organic peroxyl radicals, species that are key intermediates in many chemical processes. A special concern of this work is the study of electron transfer reactions of metalloporphyrins, which permits evaluation of these molecules as intermediates in solar energy conversion. Metalloporphyrins react with free radicals via electron transfer, involving the ligand or the metal center, or via bonding to the metal, leading to a variety of chemical species whose behavior is also investigated. The highlights of the results during the past three years are summarized below under the following sections: (a) electron transfer reactions of peroxyl radicals, concentrating on the characterization of new peroxyl radicals derived from vinyl, phenyl, other aryl, and pyridyl; (b) solvent effects on electron transfer reactions of inorganic and organic peroxyl radicals, including reactions with porphyrins, and (c) electron transfer and alkylation reactions of metalloporphyrins and other complexes.
Date: February 1, 1995
Creator: Neta, P.
Partner: UNT Libraries Government Documents Department

Retrograde reactions in coal processing: The behavior of ether and sulfide model compounds

Description: Retrograde reactions that produce more refractory molecular structures are undesirable in coal liquefaction. The authors previously found that restricted mass transport, induced by immobilization on a silica support, promotes retrograde reactions for 1,2-diphenylethane (C{sub 6}H{sub 5}CH{sub 2}CH{sub 2}C{sub 6}H{sub 5}) by both skeletal rearrangement and ring growth (cyclization-dehydrogenation) pathways involving free-radical intermediates. They are now examining the influence of heteroatoms on the retrograde pathways for the corresponding surface-immobilized ether (C{sub 6}H{sub 5}OCH{sub 2}C{sub 6}H{sub 5}) and sulfide (C{sub 6}H{sub 5}SCH{sub 2}C{sub 6}H{sub 5}) model compounds at 275--350 C. Cyclization-dehydrogenation pathways are not detected for either model compound. However, retrograde skeletal rearrangements involving 1,2-phenyl shifts in C{sub 6}H{sub 5}XCH{center_dot}C{sub 6}H{sub 5} (X = O,S) are found to be significant under restricted diffusion, and for X = O, radical coupling at ring carbons to form benzylphenols is also observed as a major pathway. For surface-immobilized benzyl phenyl ether, the two retrograde processes account for ca. 50% of the thermolysis products, and also generate reactive hydroxyl and keto functionalities that can be involved in additional retrograde reactions.
Date: April 1, 1997
Creator: Buchanan, A. C., III; Britt, P. F. & Skeen, J. T.
Partner: UNT Libraries Government Documents Department