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Ribeiro, Joao Marcelo Lamim. "Kinetics and Reaction Mechanisms for Methylidyne Radical Reactions with Small Hydrocarbons". FIU Digital Commons, 2016. http://digitalcommons.fiu.edu/etd/3023.
Pełny tekst źródłaAmyes, T. L. "Mechanisms of carboxyl-activated elimination reactions". Thesis, University of Cambridge, 1986. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.383698.
Pełny tekst źródłaWenninger, Matthias. "Sensitizing mechanisms, reaction mechanisms and reactive intermediate states in photocatalytic reactions on time scales from femto- to microseconds". Diss., Ludwig-Maximilians-Universität München, 2014. http://nbn-resolving.de/urn:nbn:de:bvb:19-176226.
Pełny tekst źródłaDie Erforschung nachhaltiger und ressourcenschonender Energiequellen bildet ein stetig wachsendes, interdisziplinäres Forschungsfeld. Neben der Photovoltaik, die inzwischen eine etablierte Energiequelle darstellt, ist die chemische Photokatalyse noch ein kleines, aber stets wachsendes Teilgebiet. In der Photokatalyse dient das einfallende Licht dazu, chemische Ver- bindungen umzuformen. Nicht nur die Anwendung der Photokatalyse für die Energiegewinnung, sondern auch der Einsatz in der chemischen Synthese stößt dabei auf wachsendes Interesse. Um photokatalytische Systeme zu optimieren ist ein fundamentales Verständnis der Prozesse erfor- derlich. Die transiente Absorptionsspektroskopie hat sich dabei als geeignetes Werkzeug erwie- sen. Der Betrieb eines Aufbaus zur Messung transienter Spektren auf verschiedenen Zeitskalen und die gezielte Datenauswertung erfordert fundiertes physikalisches und mathematisches Ver- ständnis, wohingegen die Interpretation der Ergebnisse nicht ohne chemisches Wissen erfolgen kann. Im Rahmen dieser Arbeit hat sich die Kooperation zwischen der organischen Chemie und der Physik als erfolgreiche Zusammenarbeit erwiesen. Gegenstand der vorliegenden Arbeit sind die Sensibilisierungsmechanismen, die Reaktionsmechanismen und die reaktiven Intermediate in photokatalytischer Reaktionen auf Zeitskalen von Femto- bis Mikrosekunden. Es wird gezeigt, dass die Auswertung von Datensätzen mit Standardmethoden, wie der Anpas- sung einer Summe von Exponentialfunktionen an die zeitliche Entwicklung des Signals oft nicht ausreichend ist, um die Messdaten hinreichend zu interpretieren. Erst eine der Problemstellung exakt angepasste Datenanalyse führt zum Verständnis der zugrundeliegenden Prozesse. Zunächst werden lichtinduzierte intramolekulare Ladungstransferprozesse behandelt. Die the- oretische Basis für die Beschreibung solcher Prozesse bildet die Marcus-Theorie, die kurz einge- führt wird. Anhand eines molekularen Donor-Bridge-Acceptor-Systems wird gezeigt, dass der exponentielle Dämpfungskoeffizient β oft ungeeignet ist um der Reaktion einen kohärenten Tun- nelprozess oder einen inkohärenten Transfermechanismus zuzuweisen. DNS-Haarnadelstrukturen, welche kovalent mit einem Flavin-Chromophor verbunden sind, dienen als Modellsystem für die Untersuchung intramolekularer Ladungstransferprozesse. Nach Anregung induziert Flavin eine Elektronenfehlstelle in dem benachbarten DNS-Strang, die den Strang entlangwandern kann. Es wird gezeigt, dass durch die geeignete Wahl der Basensequenz eine Quantenausbeute von ΦCS = 14 % für langlebige ladungsgetrennte Zustände erreicht wird. In einem weiteren Abschnitt wird untersucht, ob die Bausteine der DNS als chirale Umgebung für die enantioselektive Photokatalyse geeignet sind. Mit Hilfe einer auf der Marcus-Theorie basierenden Interpretation der Messergebnisse wird die konformationsabhängige Ladungstrans- ferdynamik in Benzophenon-DNS-Dinukleotiden beschrieben. Es wird gezeigt, dass die Dinuk- leotide nicht uneingeschränkt für die enantioselektive Photokatalyse geeignet sind. Schließlich wird eine echte bimolekuare photokatalytische Reaktion untersucht. Dabei wird mit Hilfe von Flavin ein Alkohol in ein Aldehyd umgesetzt. Mit einer angepassten Datenauswer- tung werden diffusive Prozesse auf der ps-Zeitskala genau quantifiziert. Die gewonnen Informa- tionen dienen dazu, die Reaktionsbedingungen zu optimieren um über einen Triplett- Reaktionsmechanismus höhere Quantenausbeuten zu erzielen. Nachdem photoinduzierte Ladungstransferprozesse ausgiebig diskutiert wurden, liegt der Fo- kus im zweiten Teil auf der [2+2] Photocycloaddition: Als Grundlage für die Interpretation spä- terer Messungen wird zunächst die [2+2] Photocykloaddition an substituierten Chinolonen unter- sucht. Die einzelnen Reaktionsschritte der Ringbildung werden auf der Zeitskala von ps bis ns quantifiziert und charakterisiert, wobei der Triplettzustand den zentralen Zustand bildet. An- schließend wird die [2+2] Photocycloaddition an substituierten Chinolonen durch einen chiralen, auf dem organischen Chromophor Xanthon basierenden Photokatalysator initiiert. Es wird ge- zeigt, dass innerhalb des Katalysator-Substrat-Komplexes, in dem beide Moleküle einen Abstand von wenigen Ångström haben, neue elektronische Eigenschaften auftreten. Die Anregung eines neuen Zustands initiiert nicht nur die [2+2] Photocycloaddition sondern stellt auch einen neuen Sensibilisierungsmechanismus dar, der bisher in photokatalytischen Reaktion organischer Mole- küle nicht beobachtet wurde. Der Triplettzustand des Chinolons tritt hierbei nicht mehr auf. Ob sich dieser Sensibilisierungsmechanismus auch auf andere Systeme übertragen lässt, muss durch weitere Arbeiten auf diesem Gebiet geklärt werden.
Smith, Dean A. "The demonstration of electron-transfer reactions and their effect on model lignin condensation reactions under alkaline pulping conditions". Diss., Georgia Institute of Technology, 1986. http://hdl.handle.net/1853/5700.
Pełny tekst źródłaChung, Lung Wa. "Computational studies of the reaction mechanisms and stereochemistry of metal-mediated organic reactions /". View abstract or full-text, 2006. http://library.ust.hk/cgi/db/thesis.pl?CHEM%202006%20CHUNG.
Pełny tekst źródłaKrug, John P. "The mechanisms of enone-alkene photocycloaddition reactions". Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1997. http://www.collectionscanada.ca/obj/s4/f2/dsk3/ftp04/nq21299.pdf.
Pełny tekst źródłaTam, Kin Yip. "Mechanisms of reactions at solid-liquid interfaces". Thesis, University of Oxford, 1996. http://ora.ox.ac.uk/objects/uuid:a7525194-433f-4bc8-914a-da452c5ffc77.
Pełny tekst źródłaBaxter, Nicholas James. "The mechanisms of reactions of #beta#-sultams". Thesis, University of Huddersfield, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.285584.
Pełny tekst źródłaLaverty, Genevieve Mary. "Kinetics and mechanisms of thermal reactions involving solids". Thesis, Queen's University Belfast, 1989. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.336105.
Pełny tekst źródłaHayden, Amy Elizabeth. "Computational studies of mechanisms and reactivities of organic reactions". Diss., Restricted to subscribing institutions, 2009. http://proquest.umi.com/pqdweb?did=1905657311&sid=1&Fmt=2&clientId=1564&RQT=309&VName=PQD.
Pełny tekst źródłaJenzer, Herbert Kurt. "Molecular mechanisms and side reactions of thyroid hormone biosynthesis /". [S.l : s.n.], 1987. http://www.ub.unibe.ch/content/bibliotheken_sammlungen/sondersammlungen/dissen_bestellformular/index_ger.html.
Pełny tekst źródłaBirrell, James Alexander. "The mechanisms of flavin site reactions in NADH:ubiquinone oxidoreductase". Thesis, University of Cambridge, 2013. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.607665.
Pełny tekst źródłaJi, Pengju. "Kinetics and mechanisms of organic reactions in liquid ammonia". Thesis, University of Huddersfield, 2011. http://eprints.hud.ac.uk/id/eprint/10033/.
Pełny tekst źródłaGordon, S. Fraser. "Investigations into the chemical and cellular mechanisms of drug hypersensitivity". Thesis, University of Liverpool, 2002. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.269702.
Pełny tekst źródłaWenninger, Matthias [Verfasser], i Eberhard [Akademischer Betreuer] Riedle. "Sensitizing mechanisms, reaction mechanisms and reactive intermediate states in photocatalytic reactions on time scales from femto- to microseconds / Matthias Wenninger. Betreuer: Eberhard Riedle". München : Universitätsbibliothek der Ludwig-Maximilians-Universität, 2014. http://d-nb.info/1062492730/34.
Pełny tekst źródłaCortés, José E. (José Enrique). "Kinetics and Mechanisms of Ligand Exchange Reactions of Chelate Complexes". Thesis, University of North Texas, 1989. https://digital.library.unt.edu/ark:/67531/metadc330827/.
Pełny tekst źródłaHammar, Peter. "Quantum Chemical Studies of Mechanisms and Stereoselectivities of Organocatalytic Reactions". Doctoral thesis, KTH, Teoretisk kemi (stängd 20110512), 2009. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-11616.
Pełny tekst źródłaQC 20100719
Somerville, Rosemarie Janet. "Mechanisms of Ni-Catalysed C–O Functionalisation and Carboxylation Reactions". Doctoral thesis, Universitat Rovira i Virgili, 2020. http://hdl.handle.net/10803/670352.
Pełny tekst źródłaComprender los mecanismos de las transformaciones catalíticas es extremadamente importante ya que esto permite a los químicos a mejorar las reacciones, por ejemplo, reduciendo la carga del catalizador, evitando la formación de subproductos u obteniendo conocimiento fundamental sobre la estructura y la unión de los intermedios. El objetivo de esta tesis radica en las transformaciones desarrolladas recientemente de la funcionalización C-O catalizada por Ni y las reacciones de acoplamiento reductor catalizadas por Ni. Si bien estas reacciones se ven facilitadas por las propiedades favorables de Ni en comparación con Pd, el alcance de los posibles mecanismos para una reacción catalizada por Ni es más amplio y se conoce menos información sobre sus mecanismos en comparación con las transformaciones catalizadas por Pd. Los desafíos para comprender las características mecanicistas incluyen intermedios potencialmente inestables, la necesidad de datos cinéticos confiables y el análisis de las numerosas propuestas mecanicistas que se han presentado. En este trabajo, se presentan tres instantáneas mecanicistas de estas transformaciones catalizadas por Ni. El primero es un amplio estudio mecanicista de la sililación C-O catalizada por Ni de ésteres de arilo, donde se informan los primeros complejos de adición oxidativa de Ni y ésteres de arilo con una fosfina monodentada. El segundo es una investigación sobre un intermedio propuesto en las reacciones de acoplamiento reductor: un complejo de Ni (I) -alquilo. Un ejemplo fue aislado y caracterizado por EPR y cristalografía de rayos X. Significativamente, su reactividad de inserción de CO2 también fue probada. El tercer proyecto arroja luz sobre el papel de Zn como algo más que un reductor en la carboxilación catalizada por Ni de sales de arilsulfonio.a
Understanding the mechanisms of catalytic transformations is extremely important as this allows chemists to improve reactions by, for example, reducing catalyst loading, preventing the formation of by-products, or obtaining fundamental knowledge about the structure and bonding of intermediates. The focus of this thesis lies with the recently developed transformations of Ni-catalysed C–O functionalisation and Ni-catalysed reductive coupling reactions. Whilst these reactions are facilitated by the favourable properties of Ni compared to Pd, the scope of possible mechanisms for a Ni-catalysed reaction is broader and less information is known about their mechanisms compared to Pd-catalysed transformations. Challenges in understanding mechanistic features include potentially unstable intermediates, a need for reliable kinetic data, and parsing the many mechanistic proposals that have been put forward. In this work, three mechanistic snapshots of these Ni-catalysed transformations are presented. The first is a broad mechanistic study of the Ni-catalysed C–O silylation of aryl esters, where the first oxidative addition complexes of Ni and aryl esters with a monodentate phosphine are reported. The second is an investigation into a proposed intermediate in reductive coupling reactions – a Ni(I)-alkyl complex. One example was isolated and characterised by EPR and X-ray crystallography. Significantly, its CO2 insertion reactivity was also probed. The third project sheds light on the role of Zn as more than just a reductant in the Ni-catalysed carboxylation of arylsulfonium salts.
Gunnarsson, Iva. "SLE : pathogenetic mechanisms in nephritis and sulphasalazine-induced lupus reactions /". Stockholm, 1999. http://diss.kib.ki.se/1999/91-628-3654-4/.
Pełny tekst źródłaPurser-Hallard, Beatrice. "Kinetics and mechanisms of solid-state phase transitions and reactions". Thesis, Open University, 2005. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.422026.
Pełny tekst źródłaCochain, Benjamin, V. Magnien, Daniel R. Neuville i Pascal Richet. "Diffusion in silicate melts: kinetics and mechanisms of redox reactions". Diffusion fundamentals 6 (2007) 77, S. 1, 2007. https://ul.qucosa.de/id/qucosa%3A14257.
Pełny tekst źródłaHao, Weifang. "The Mechanisms of Hydride Exchange, Organic Combination and Displacement Reactions". DigitalCommons@USU, 2012. https://digitalcommons.usu.edu/etd/1226.
Pełny tekst źródłaRule, Krista Lynn. "The Mechanisms, Products, and Kinetics of Triclosan-Free Chlorine Reactions". Thesis, Virginia Tech, 2004. http://hdl.handle.net/10919/42791.
Pełny tekst źródłaMaster of Science
Kotcharaksa, Komgrit. "The Mechanisms, Products, and Kinetic of Carbamazepine-Free Chlorine Reactions". Thesis, Virginia Tech, 2008. http://hdl.handle.net/10919/36422.
Pełny tekst źródłaMaster of Science
Zhuang, Yipping. "Mechanisms of alkane reactions over platinum and tungsten carbide catalysts". Doctoral thesis, Universite Libre de Bruxelles, 1995. http://hdl.handle.net/2013/ULB-DIPOT:oai:dipot.ulb.ac.be:2013/212599.
Pełny tekst źródłaFardost, Ashkan. "Palladium(II)-Catalyzed Heck Reactions : Domino Reactions, Decarboxylations, Mechanistic Studies & Continuous Flow Applications". Doctoral thesis, Uppsala universitet, Institutionen för läkemedelskemi, 2015. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-242259.
Pełny tekst źródłaDeary, Michael Edward. "Peroxide bleach activation: kinetics and mechanisms of some acyl transfer reactions". Thesis, Northumbria University, 1991. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.493973.
Pełny tekst źródłaBoakes, Gavin. "Kinetics and mechanisms of halogen reactions involved in atmospheric ozone depletion". Thesis, University College London (University of London), 2004. http://discovery.ucl.ac.uk/1446700/.
Pełny tekst źródłaPower, Nicholas Patrick. "Kinetics and mechanisms of reactions of N-arylsulfonyl derivatives of imines". Thesis, University of Ulster, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.267781.
Pełny tekst źródłaHanly, Ann Marie. "Mechanisms of reactions of N-arylsulfonyl derivatives of imines and oxaziridines". Thesis, University of Ulster, 1994. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.260538.
Pełny tekst źródłaGu, Xiaodong. "Oxidative lipid fragmentation; New mechanisms, synthesis and reactions of putative intermediates". Case Western Reserve University School of Graduate Studies / OhioLINK, 2010. http://rave.ohiolink.edu/etdc/view?acc_num=case1275497811.
Pełny tekst źródłaZapico, Alvarez David. "Mechanisms and kinetics of the galvannealing reactions on Ti IF steels". Thesis, Châtenay-Malabry, Ecole centrale de Paris, 2014. http://www.theses.fr/2014ECAP0019.
Pełny tekst źródłaHot-Dip GalvAnnealed (HDGA) coatings are produced by the immersion of the steel strip into an iron-saturated liquid zinc bath at around 460 °C containing small amounts of aluminium (from 0.1 to 0.135 wt.%, normally) and its subsequent heating (up to temperatures around 500-530 °C for about 10 s, typically) in order to trigger the alloying reactions between iron and zinc. The final microstructure of this kind of coatings is composed of a sequence of stratified Fe-Zn phase layers and its in-use properties are directly related to the phase distribution within the coating. The process parameters to be performed in industrial lines must therefore be optimized in order to obtain a successful coating microstructure with the minimum costs. The development of such a coating passes through different and complex reactions: the inhibition layer formation, the inhibition layer breakdown, the liquid zinc consumption and the iron enrichment of the solid coating. The kinetics accounting for these reactions must be studied and modelled separately in order to accurately control the evolution of the coating along the heat treatment performed in the industrial line. In the present work, the two first reactions were investigated in the case of Ti IF steel grades. The kinetics of the inhibition layer formation is extremely fast and has therefore not been investigated in detail. Concerning this reaction, the focus was given to the nature of this inhibition layer and to the mechanisms accounting for its formation. It has been found that the inhibition layer formed in typical baths for galvannealed coatings production is composed of a very thin layer of the Fe2Al5Znx phase (20-30 nm) on the steel surface and a thicker layer of the δ (FeZn7) phase (around 200 nm) on its top. As the steel strip enters the zinc bath, iron dissolution from the former into the latter leads to an iron supersaturation at the solid / liquid interface. As a result, a very thin layer of metastable Fe2Al5Znx nucleates on the steel surface favoured by preferential epitaxial relationships with ferrite. Subsequently, δ nucleates on the Fe2Al5Znx layer allowing the final microstructure of the inhibition layer to become thermodynamically stable. The effect of the bath aluminium content on the nature of this inhibiting structure has also been studied. As the bath aluminium content is lowered, the Fe2Al5Znx layer becomes discontinuous: the lower the bath aluminium content is, the higher the metastability of Fe2Al5Znx is and the less probable its nucleation on the steel surface is. The inhibition state is only transient and continued heat treatment will lead to the inhibition layer breakdown and the development of the further Fe-Zn alloying reactions. The breakdown mechanism, controlled by the diffusion of zinc towards the steel grain boundaries, can be explained using the Al-Fe-Zn ternary phase diagram and summarized in two steps: the disappearance of the Fe2Al5Znx layer at the inhibition layer / steel interface as a result of the enrichment of this interface in zinc, and the local nucleation of the Г (Fe3Zn10) phase at the steel grain boundaries, breaking the inhibition layer off, when the zinc concentration at these locations becomes high enough. The kinetics accounting for this reaction strongly depends on the Ti IF steel chemical composition and the bath aluminium content. On the one hand, it has been found that the effect of the steel chemical composition on the inhibition layer breakdown kinetics would be ruled by the competition between two opposite phenomena: the rate of zinc diffusion at the steel grain boundaries and the ability of the steel to accumulate the zinc atoms at these locations On the other hand, decreasing the bath aluminium content favours the discontinuity of Fe2Al5Znx, which accelerates the inhibition layer breakdown as zinc is expected to diffuse faster through δ than through Fe2Al5Znx
Tan, Kristine Joy Wei Mei. "Thiyl radical reactions with alkynes in the absence and presence of oxygen". Connect to thesis, 2009. http://repository.unimelb.edu.au/10187/7036.
Pełny tekst źródłaIn addition, the reactions of benzylthiyl, tert-butylthiyl and allylthiyl radicals with cyclodecyne (1) were investigated. Various sources of thiyl radical generation were utilized, such as the photolysis of disulfides and thiols, hydrogen atom abstraction of thiols using radical initiators, as well as thiol autoxidation in the presence of oxygen. The radical cascade initiated by the addition of thiyl radicals to alkyne 1 was typically terminated by either reduction or disproportionation, whereas “self-termination” was only observed in one particular instance where the tert-butylthiyl radical was generated by autoxidation. However, this was only a minor pathway.
The second objective of this work was to investigate the reactions of thiyl radicals with alkynes in the presence of oxygen. For this purpose, phenylthiyl radicals were generated in the presence of diphenylacetylene (89) and molecular oxygen. Benzil (91), an α-diketone, and 1,2-diphenyl-2-(phenylthio)ethanone (93), an α-ketosulfide, were formed. The novel thiyl radical-mediated oxidation of diphenylacetylene to benzil mediated proceeds under mild and metal-free conditions, using various methods of thiyl radical generation. The product ratio of diketone to ketosulfide varied with the reaction conditions. Under photochemical conditions, benzil was formed but its photodegradation was also observed. Using autoxidation, moderate to good yields of both diketone 91 and ketosulfide 93 were obtained, although the product ratios varied with solvent and reaction conditions. Diketone 91 was the major product when the thiyl radical was generated electrochemically. Following investigation of the reaction mechanism using experimental and computational studies, the phenylthiyl peroxyl radical was identified as the key reactive intermediate. This represents the first synthetic application of thiyl peroxyl radicals.
Using autoxidation conditions, the oxidation was explored using substituted aromatic thiyl radicals, e.g. 2,6-dimethylbenzene, 2,4,6-tri-tert-butylbenzene, 4-methoxybenzene and 4-nitrobenzene thiyl radicals. Except for the case of 4-methoxybenzene thiyl radicals, where generation of the thiyl radicals was inefficient, diketone 91 was formed as the dominant product. This oxidation of alkynes to ketones, via thiyl radical-mediated activation of oxygen, was then applied to cyclodecyne (1). Bicyclic ketones 7/8 were found as the major products under photochemical conditions, while sulfides 152/trans-49a were the dominant products under autoxidation conditions. Bicyclic ketones 7/8 were formed due to the intramolecular radical processes directed by the transannular strain of the ten-membered carbon framework. Only trace amounts of the cyclic α-diketone 151 were detected under autoxidation conditions.
Becker, Bruce. "Investigation of heavy ion reaction mechanisms by means of the inclusive 93Nb(12C,7Be) and 93Nb(12C,9Be) reactions". Master's thesis, University of Cape Town, 2002. http://hdl.handle.net/11427/6993.
Pełny tekst źródłaInclusive continuum cross-sections for the reactions 93Nb(12C,7Be) and 93Nb(12C,9Be) were measured at the NAC using a ΔE - E setup. A theoretical light output model which could account for the mass and charge dependance of the NaI E detectors was employed to calibrate the NaI(TI) detectors. The model is outlined and it is shown that the nonlinearity of the detector response is only due to a term which describes the mass-dependance. Investigation of the cross-sections revealed interesting facts about the dominant reaction mechanisms in the interaction of 120 with heavy targets. A theoretical model developed by the Milano group has been very successful in describing the continuum cross-sections of a particles (including 9Be) created in similar reactions of 120 and 160, incident on heavy targets. The analysis shows that the same description of the continuum cross-sections of 7Be and 9Be gives good agreement with the data (with different energy-loss parameters and survival probabilities), although there are discrepancies, especially at the lower incident angles. These small discrepancies may indicate the presence of a multistep direct reaction between the detected fragment and the residual nucleus in the exit channel. The most notable result of the analysis of the data was that the spectra of 7Be and 9Be, previously suspected to be created in a final-state interaction of sBe with the residual nucleus, are well-described by a friction-dissipative breakup mechanism.
Zeng, Xiaofeng. "Mechanisms for Solvolytic Elimination and Substitution Reactions Involving Short-lived Carbocation Intermediates". Doctoral thesis, Uppsala University, Organic Chemistry, 2002. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-2565.
Pełny tekst źródłaSolvolysis reactions of a range of tertiary substrates in largely aqueous solvents were studied in such respects as β-deuterium kinetic isotope effects, linear free energy relationships and stereochemistry.
Solvolysis of the fluorene derivatives 9-methyl–9-(2´-X-2´-propyl)fluorene (1-X, X = Cl, Br, OOCCF3) involves a very short-lived carbocation intermediate. The fraction of alkene is increased by addition of general bases, which can be expressed by a Brφnsted parameter β = 0.07. The kinetic deuterium isotope effects vary with solvent composition in a way which is not consistent with a common carbocation intermediate which has time to choose between dehydronation and addition of a solvent water molecule.
In the absence of bases, the reaction of 4-chloro-4-(4´-nitrophenyl)pentan-2-one (2-Cl) proceeds through a short-lived carbocation intermediate yielding 4-(4´-nitrophenyl)-2-oxopent-4-ene (2-t-ne)as the main elimination product. Addition of acetate ion and other weak bases results in the base-promoted E2 (or E1cb) reaction to give (E)-4-(4´-nitrophenyl)-2-oxopent-3-ene (2-E-ne) and (Z)-4-(4´-nitrophenyl)-2-oxopent-3-ene(2-Z-ne). There is no evidence for a water-promoted E2 (or E1cb) reaction.
The stereochemistry studies of elimination from (R,S and S,R)-[1-(3´-fluoro)phenyl-2-methyl]cyclopentyl-p-nitrobenzoate (3-PNB) and its (R,R and S,S)isomer 3´-PNB and (R,S and S,R)-[1´-(3´´-fluoro)phenyl-2´-methylcyclopentyl]-2,2,2-trifluoroacetate(3-OOCCF3) exclude the concerted pericyclic elimination mechanism for formation of the alkene 1-(3´-fluoro)phenyl-2-methylcyclopentene(3-m-ne). The effects of added thiocyanate ion and halide ions on the solvolysis reaction are discussed.
Mass spectrometry analysis showed complete incorporation of the labeled oxygen from solvent water into the product 2-hydroxy-2-phenyl-3-butene (4-OH), confirming that it is the tertiary carbon-oxygen bond that is broken in the acid-catalyzed solvolysis of 2-methoxy-2-phenyl-3-butene (4-OMe). The mechanism for the dominant formation of the less stable 4-OH is discussed.
Gomez, David [Verfasser], i Stefan [Akademischer Betreuer] Klumpp. "Mechanisms of biochemical reactions within crowded environments / David Gomez ; Betreuer: Stefan Klumpp". Potsdam : Universität Potsdam, 2016. http://d-nb.info/1218400757/34.
Pełny tekst źródłaKing, Martin D. "Kinetics and mechanisms of reactions of NOâ†3 with some biogenic species". Thesis, University of Oxford, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.299017.
Pełny tekst źródłaDemirtas, Ibrahim. "Synthesis and mechanisms of reactions of substituted N-tritylamines and related compounds". Thesis, University of Newcastle Upon Tyne, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.389591.
Pełny tekst źródłaJones, John David. "The role of direct and indirect dynamical mechanisms in reactions at surfaces". Thesis, University of Southampton, 1994. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.259624.
Pełny tekst źródłaBreno, Kerry L. "Organometallic catalysis in aqueous solution : reactions and mechanisms of water-soluble molybdocenes /". view abstract or download file of text, 2004. http://wwwlib.umi.com/cr/uoregon/fullcit?p3120612.
Pełny tekst źródłaTypescript. Includes vita and abstract. Includes bibliographical references (leaves 213-252). Also available for download via the World Wide Web; free to University of Oregon users.
Fuller, Jack Terrell. "Computational Studies on Mechanisms and Reactivity of Mercury and Cobalt Organometallic Reactions". BYU ScholarsArchive, 2016. https://scholarsarchive.byu.edu/etd/5974.
Pełny tekst źródłaLi, Zhao. "The Kinetics and Mechanisms of Some Fundamental Organic Reactions of Nitro Compounds". DigitalCommons@USU, 2012. https://digitalcommons.usu.edu/etd/1407.
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Pełny tekst źródłaBarradas, Gonçalo. "A Cross-Cultural Approach to Psychological Mechanisms Underlying Emotional Reactions to Music". Doctoral thesis, Uppsala universitet, Institutionen för psykologi, 2017. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-314870.
Pełny tekst źródłaJiménez, Halla José Óscar Carlos. "Theoretical study of catalytic reactions of carbenes: haptotropic rearrangements and the Dötz reaction". Doctoral thesis, Universitat de Girona, 2009. http://hdl.handle.net/10803/7942.
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Pełny tekst źródłaWilliams, Robert Earl Jr. "Simulation and Characterization of Cathode Reactions in Solid Oxide Fuel Cells". Diss., Georgia Institute of Technology, 2007. http://hdl.handle.net/1853/16309.
Pełny tekst źródłaAli, Fawzia Runa. "Mechanisms of Late Asthmatic Reactions Induced By Inhalation of T Cell Peptide Epitopes". Thesis, Imperial College London, 2007. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.498866.
Pełny tekst źródłaAllgäuer, Dominik. "Kinetics and mechanisms of the reactions of nitrogen ylides with acceptor-substituted olefins". Diss., Ludwig-Maximilians-Universität München, 2014. http://nbn-resolving.de/urn:nbn:de:bvb:19-181637.
Pełny tekst źródłaJi, Yongfei. "Theoretical Studies on the Molecular Mechanisms of Photo-Catalytic Reactions on TiO2 Surfaces". Doctoral thesis, KTH, Teoretisk kemi och biologi, 2014. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-145146.
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