To see the other types of publications on this topic, follow the link: Carbon compounds.
Dissertations / Theses on the topic 'Carbon compounds'
Create a spot-on reference in APA, MLA, Chicago, Harvard, and other styles
Consult the top 50 dissertations / theses for your research on the topic 'Carbon compounds.'
Next to every source in the list of references, there is an 'Add to bibliography' button. Press on it, and we will generate automatically the bibliographic reference to the chosen work in the citation style you need: APA, MLA, Harvard, Chicago, Vancouver, etc.
You can also download the full text of the academic publication as pdf and read online its abstract whenever available in the metadata.
Browse dissertations / theses on a wide variety of disciplines and organise your bibliography correctly.
1
Wen, Ting Bin. "Alkyne activation and carbon-carbon bond formation mediated by osmium complexes /." View Abstract or Full-Text, 2003. http://library.ust.hk/cgi/db/thesis.pl?CHEM%202003%20WEN.
Full text
2
Koutsantonis, George Anthony. "Some organotransition metal chemistry of the carbon-carbon triple bond /." Title page, contents and summary only, 1989. http://web4.library.adelaide.edu.au/theses/09PH/09phk876.pdf.
Full text
3
Laffosse, Miguel Diaz. "Stereoselective carbon-carbon bond formation via sulfur stabilized carbanions." Thesis, Georgia Institute of Technology, 1985. http://hdl.handle.net/1853/27171.
Full text
4
Liang, Jianglin, and 梁江林. "Ruthenium-catalyzed carbon-nitrogen bond formations." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2003. http://hub.hku.hk/bib/B31245729.
Full text
5
Murphy, Brian Timothy. "Isotopomeric carbon compounds in star formation regions." Thesis, University of Kent, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.270812.
Full text
6
Kommagalla, Y. "[Metal]–catalyzed carbon–carbon and carbon– heteroatom bond formation: synthesis of biologically active heterocyclic compounds." Thesis(Ph.D.), CSIR-National Chemical Laboratory, Pune, 2014. http://dspace.ncl.res.in:8080/xmlui/handle/20.500.12252/2214.
Full text
7
Bronk, Brian Scott 1967. "New methods for the formation of carbon-carbon bonds via organometallic compounds." Thesis, Massachusetts Institute of Technology, 1995. http://hdl.handle.net/1721.1/35441.
Full text
8
Sze, Fan Fu. "Enhanced abatement of aqueous organic compounds using stratified activated carbon adsorption columns /." View abstract or full-text, 2009. http://library.ust.hk/cgi/db/thesis.pl?CBME%202009%20SZE.
Full text
9
Holmes, Brett. "Mobilization of Metals and Phosphorous from Intact Forest Soil Cores by Dissolved Inorganic Carbon: A Laboratory Column Study." Fogler Library, University of Maine, 2007. http://www.library.umaine.edu/theses/pdf/HolmesB2007.pdf.
Full text
10
Destro, Gianluca. "Chemistry of CO₂ for the synthesis of radio-labelled compounds." Thesis, Université Paris-Saclay (ComUE), 2019. http://www.theses.fr/2019SACLS228.
Full textAbstract:
Le marquage radioisotopique est un domaine d’intérêt d’un point de vue de la recherche fondamentale en santé et, de par ses nombreuses applications, aussi bien en industrie pharmaceutique et agrochimique que dans le milieu académique. Dans ce contexte, le carbone-14 joue un rôle primordial dans le développement de nouvelles drogues et dans les études ADME et toxicologiques. Les voies de synthèse traditionnelles impliquant le ¹⁴C sont longues et multi-étapes ce qui entrave la viabilité de cette stratégie. L’objectif de cette thèse est de développer de nouvelles techniques de radiomarquage par échange isotopique. Dans un premier temps, nos efforts se sont portés sur le développement d’un échange d’isotopes du carbone (EIC) dynamique entre le ¹³CO₂ ou le ¹⁴CO₂, une source fondamentale et facile d’accès de carbone radioactifs et des acides carboxyliques (hétéro)aromatiques par le biais d’une catalyse au cuivre. Le concept de EIC a ensuite été appliqué à d’autres fonctions, présentes dans de nombreux agents pharmaceutiques, les acides phénylacétiques. Une nouvelle approche, sans métaux de transition, a pu être décrite, permettant d’effectuer le marquage avec le ¹³CO₂, le ¹⁴CO₂ et le ¹¹CO₂. Enfin, un autre EIC faisant intervenir le cyanure comme source primaire de carbone radioactif a été conçu. Le développement de l’EIC a permis d’étendre le concept de marquage en dernière étape de synthèse à des substrats contenant une fonction nitrile ou acide carboxylique, en réduisant les coûts et en limitant la génération de déchets radioactifs. Ce concept, encore en voie de développement, offre des alternatives aux méthodes existantesRadioisotope labeling is a relevant topic both from a fundament research perspective and for health applications in academy and pharmaceutical and agrochemical industries. In this context, carbon-14 plays a basic role in drug development and ADME and toxicological studies. Traditional synthesis with radiocarbon (¹⁴C), based on lengthy and multistep approaches, have hampered the sustainable of the strategy. The aim of this thesis is to develop novel labeling techniques by isotope exchange. At first, our efforts were focused on the developement of a copper catalyzed dynamic carbon isotope exchange (CIE) using ¹³CO₂ and ¹⁴CO₂, a fundamental and readily available source of radiocarbon on (hetero)aromatic carboxylic acids. The concept of CIE was further extent to another relevant drug scaffolds such as phenyl acetic acids. Hence, it was described a transition metal-free approach able to exchange ¹³CO₂, le ¹⁴CO₂ and ¹¹CO₂, to the best of our knowledge this would be the first example. At last, another CIE with a different primary radiocarbon source such as cyanyde was envisioned. CIE technology expands the concept of late-stage carbon radiolabeling, with substrates bearing carboxylic acid and nitrile moieties, reducing the synthetic costs and limiting the generation of radioactive waste. This new process is still at its infancy and more work need to be done
11
Crumpton, Dawn M. "Mechanistic studies of carbon-carbon and carbon-hydrogen reductive elimination reactions from platinum(IV) complexes /." Thesis, Connect to this title online; UW restricted, 2000. http://hdl.handle.net/1773/8484.
Full text
12
Hung, Wai Yiu. "Syntheses and reactivities of osmium and ruthenium complexes with metal-carbon triple bonds /." View abstract or full-text, 2006. http://library.ust.hk/cgi/db/thesis.pl?CHEM%202006%20HUNG.
Full text
13
Frankowski, Kevin J. "Carbenes and carbenoids as powerful tools in organic synthesis." Access to citation, abstract and download form provided by ProQuest Information and Learning Company; downloadable PDF file 2.18 Mb., 94 p, 2006. http://gateway.proquest.com/openurl?url_ver=Z39.88-2004&res_dat=xri:pqdiss&rft_val_fmt=info:ofi/fmt:kev:mtx:dissertation&rft_dat=xri:pqdiss:3205422.
Full text
14
Hinrichs, Heino. "Ethynyl[2.2]paracyclophanes building blocks for carbon rich compounds /." [S.l.] : [s.n.], 2005. http://deposit.ddb.de/cgi-bin/dokserv?idn=975728342.
Full text
15
Archbold, M. E. "Carbon isotopes of volatile organic compounds for environmental tracing." Thesis, Queen's University Belfast, 2005. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.419452.
Full text
16
Berg, Elin. "Adsorption of organic andinorganic compounds onactivated carbon and biochar." Thesis, Umeå universitet, Kemiska institutionen, 2017. http://urn.kb.se/resolve?urn=urn:nbn:se:umu:diva-136631.
Full text
17
Song, Weining. "Some aspects of the utilization of inorganic nitrogen compounds and carbon compounds by "Nitrobacter hamburgensis" /." Title page, contents and summary only, 1987. http://web4.library.adelaide.edu.au/theses/09A/09as724.pdf.
Full text
18
Lau, Clifford James. "A study of several interesting carbocyclic molecules /." The Ohio State University, 1987. http://rave.ohiolink.edu/etdc/view?acc_num=osu1487584612166485.
Full text
19
Cummings, Edward A. "A study of amperometric biosensors of phenolic compounds." Thesis, University of Ulster, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.342389.
Full text
20
Hunter, James Freeman. "Oxidation of atmospheric organic carbon : interconnecting volatile organic compounds, intermediate-volatility organic compounds, and organic aerosol." Thesis, Massachusetts Institute of Technology, 2015. http://hdl.handle.net/1721.1/97794.
Full textAbstract:
Thesis: Ph. D. in Environmental Chemistry, Massachusetts Institute of Technology, Department of Civil and Environmental Engineering, 2015.Cataloged from PDF version of thesis.
Includes bibliographical references (pages 101-110).
.Organic molecules have many important roles in the atmosphere, acting as climate and biogeochemical forcers, and in some cases as toxic pollutants. The lifecycle of atmospheric organic carbon is extremely complex, with reaction in multiple phases (gas, particle, aqueous) and at multiple timescales. The details of the lifecycle chemistry (especially the amount and properties of particles) have important implications for air quality, climate, and human and ecosystem health, and need to be understood better. Much of the chemical complexity and uncertainty lies in the reactions and properties of low-volatility oxidized intermediates that result from the oxidation of volatile organic precursors, and which have received comparatively little study thus far. This thesis describes three projects that link together the entire chain of oxidation (volatile to intermediate to condensed) in an effort to improve our understanding of carbon lifecycle and aerosol production. Laboratory studies of atmospherically relevant aerosol precursors show that the slow oxidation of intermediates is critical to explaining the yield and properties of aerosol under highly oxidized ("aged") conditions, and that the production of organic particles is significantly increased when intermediates are fully oxidized. This aging process is a strong function of molecular structure, and depends on aerosol concentration through the phenomenon of condensational trapping. Further laboratory studies of a series of (poly)cyclic 10 carbon alkanes show that structural effects are largely explained through fragmentation reactions, and that more generally, carbon-carbon bond scission is a ubiquitous and important reaction channel for oxidized intermediates. Finally, direct measurement of oxidized intermediate compounds in field studies shows that these compounds are abundant and important in the ambient atmosphere, with concentrations and properties in between those of volatile and particulate organic compounds. Together with other co-located measurements and complementary techniques, this enables estimates of emission, oxidation, and deposition to be constructed. The results from this thesis can be used to inform more sophisticated models of atmospheric organic carbon cycling, and to improve prediction of organic particulate matter concentrations.
by James Freeman Hunter.
Ph. D. in Environmental Chemistry
21
Carter, Robin. "Structural analysis of semiconductor compounds in single walled carbon nanotubes." Thesis, University of Oxford, 2004. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.419250.
Full text
22
Bratt, Mark. "The synthesis of carbonates and related compounds from carbon dioxide." Thesis, University of Warwick, 2001. http://wrap.warwick.ac.uk/62120/.
Full textAbstract:
The manufacture of carbonates and carbamates is essential due to their wide range of applications from polymers in foams, elastomers and engineering plastics to agrochemicals. Since there is a high demand for both types of compound, there is a commercial justification for use of phosgene in their synthesis. However, phosgene is highly toxic in small quantities. The development of an alternative reagent is therefore most desirable. This thesis relates our attempts to overcome the problem of phosgene use by utilising C02. Chapter One highlights previous research concerning the synthesis of carbonates and their derivatives from CO2. Chapter Two details the development of the reaction of CO2 to form methanesulfonyl carbonates (RO(CO)OS02Me) and carbamates (R2N(CO)OS02Me), which are precursors of carbonates and carbamates respectively. Alcohols or amines are reacted with CO2 at atmospheric pressure in acetonitrile to generate carbonate and carbamate anions in situ. Reaction with methanesulfonic anhydride leads to the methanesulfonyl carbonates and carbamates which are observed spectroscopically but are not isolable. Chapter Three explains the successful conversion of methanesulfonyl carbonates and carbamates to carbonates and carbamates, as well as testing the scope of the reaction. Chapter Four demonstrates the transfer of the synthetic methodology to multifunctional compounds to generate dendritic carbamates and highlights the various approaches used to achieve this goal. Chapter Five is the experimental section.
23
Lasota, Maria Jacinta. "Oxidative degradation of aniline derived compounds over carbon based materials." Master's thesis, Instituto Politécnico de Bragança, Escola Superior de Tecnologia e Gestão, 2010. http://hdl.handle.net/10198/2266.
Full textAbstract:
The objectives of this work were: the preparation of different forms of carbon materials (AC, ACSA, CX, CXSA and GBCM), assessment of their catalytic efficiency in the CWPO of the azo dye Chromotrope 2R.
Initially the materials were characterized by several techniques, afterwards adsorption and reaction runs were done and lastly the samples obtained from the adsorption/reaction runs were tested using the COD to calculate the organic matter in solution.
Reactions were carried out with 100 mg/L C2R solution at 50ºC, pH = 3, hydrogen peroxide of 34.6 mM (5 mL) and 0.5 g/L of carbon material. Several samples (5 mL) were removed from the reactor during 2.5 hours to evaluate the evolution of the dye removal by analysis with UV-VIS (spectrophotometer). The adsorption runs were done the same way, but without hydrogen peroxide.
The best results were obtained with Activated Carbon, this material was the best adsorbing material and catalyst, removing 64 % of C2R after 150min of reaction and 74 % the adsorption run.
As the reaction results weren´t better than the adsorption ones, iron was incorporated in two of the materials. Incorporating iron in the carbon materials increased radically their catalytic behaviour, with 100 % removal being attained after 150 min of reaction. Os objectivos deste trabalho foram: a preparação de diferentes materiais de carbono (AC, ACSA, CX, CXSA e GBCM) e testar a eficiência destes no CWPO do corante Chromotrope 2R.
Inicialmente os materiais foram caracterizados através de várias técnicas, seguidamente foram realizados os ensaios de adsorção e reacção, e no fim, determinou-se a Carência Química do Oxigénio (CQO) das amostras resultantes dos ensaios.
As reacções foram feitas numa solução de Chromotrope a 100 mg/L, a 50º C, pH = 3, peróxido de hidrogénio a 34.6 mM (5 mL) e com 0.5 g/L de material de carbono. Foram retiradas várias amostras (5 mL) do reactor durante 2.5 horas, para avaliar a evolução da degradação do corante através da análise com UV-VIS (espectrofotómetro). Os ensaios de adsorção foram feitos da mesma forma, mas sem o peróxido de hidrogénio.
Os melhores resultados foram obtidos com o carvão activado que foi o melhor adsorvente e catalisador, removendo 64 % do Chromotrope após 150 min de reacção e 74 % no ensaio de adsorção.
Como os resultados da reacção não foram melhores que os obtidos da adsorção, foi incorporado ferro em dois dos materiais. A incorporação de ferro nos materiais de carbono aumentou radicalmente o comportamento catalítico destes, obtendo-se uma remoção de 100 % após 150 min de reacção.
24
Yoshii, Takao. "Structures and Electronic Properties of Carbon Clusters and Related Compounds." Kyoto University, 2001. http://hdl.handle.net/2433/150661.
Full text
25
Zhou, Guanliang. "Photocatalytic degradation of organic compounds using carbon based composite catalysts." Thesis, Curtin University, 2013. http://hdl.handle.net/20.500.11937/1328.
Full textAbstract:
In recent decades, the applications of advanced oxidation processes (AOPs) for organic pollutants treatment in wastewater have been thoroughly investigated. These techniques base on chemical destruction and give a complete solution to the problem of wastewater containing toxic organics. Among these processes, semiconductor-based photocatalytic process has been employed as a low-cost, environmentally friendly and sustainable technique to purify water/wastewater. Meanwhile, chemical oxidation process is also considered as an effective remediation technique to reduce the concentrations of targeted toxic organics in wastewater to acceptable levels.The aim of this work is emphasizing the role of new synthesized catalysts in advanced oxidation process for wastewater treatment. The key conclusion of this thesis is that novel photocatalysts being capable to degrade organics in aqueous phase at room temperature were successfully synthesized and the investigation of “green cobalt based catalysts” for degradation of organic pollutants via advanced oxidation processes was achieved. Various types of catalysts were synthesized with hydrothermal carbonization method or wet impregnation method, and used for degradation of phenol in aqueous phase with UV-vis and visible light irradiation. Titanates: ZnTiO3, FeTiO3 and Bi4Ti3O12 were modified by coating cobalt (Co) to prepare photocatalysts. Microcarbon spheres were also synthesized by hydrothermal method, and used to support TiO2 (C-TiO2), nanoscaled zerovalent iron (nano-Fe0@CS), cobalt (micro-CS@Co) and graphitic carbon nitride (C-g-CN). All of these catalyst materials were tested for phenol degradation. Some of these synthesized catalysts were also examined for activating peroxymonosulfate (PMS, Oxone) for the decomposition of phenol.
26
Aydın, Mustafa Elmacı Nuran. "Quantum Chemical Investigations On Acetylenic Carbon Rich Compounds As Molecular Construction Kit/." [s.l.]: [s.n.], 2004. http://library.iyte.edu.tr/tezler/master/kimya/T000438.doc.
Full text
27
Chen, Jinshui. "Studies on Transition Metal-catalyzed Carbon－Carbon Bond Forming Reactions through Intramolecular Activation of Organosilicon Compounds." 京都大学 (Kyoto University), 2008. http://hdl.handle.net/2433/57272.
Full textAbstract:
Kyoto University (京都大学)0048
新制・課程博士
博士(工学)
甲第13828号
工博第2932号
新制||工||1433(附属図書館)
26044
UT51-2008-C744
京都大学大学院工学研究科材料化学専攻
(主査)教授 檜山 爲次郎, 教授 大嶌 幸一郎, 教授 松原 誠二郎
学位規則第4条第1項該当
28
Maeda, Yasunari. "Studies on vanadium-, palladium-, and copper-catalyzed oxidation and carbon-carbon bond cleavage of organic compounds." 京都大学 (Kyoto University), 2005. http://hdl.handle.net/2433/144888.
Full textAbstract:
Kyoto University (京都大学)0048
新制・課程博士
博士(工学)
甲第11533号
工博第2479号
新制||工||1336(附属図書館)
23176
UT51-2005-D283
京都大学大学院工学研究科物質ｴﾈﾙｷﾞｰ化学専攻
(主査)教授 光藤 武明, 教授 檜山 爲次郎, 教授 大江 浩一
学位規則第4条第1項該当
29
Bravo-Altamirano, Karla. "New methodologies for the preparation of organophosphorus compounds via carbon-phosphorus bond formation." Fort Worth, Tex. : Texas Christian University, 2007. http://etd.tcu.edu/etdfiles/available/etd-04252007-115357/unrestricted/bravo.pdf.
Full text
30
Carss, Steven Andrew. "High-resolution NMR studies of solid halogenated organic compounds." Thesis, Durham University, 1995. http://etheses.dur.ac.uk/5208/.
Full textAbstract:
This thesis is a study of solid halogenated organic compounds by Nuclear Magnetic Resonance Spectroscopy (NMR) in an attempt to extract previously inaccessible information. The first part of the thesis is concerned with three fluorinated steroids, studied by observing (^1)H, (^13)C and (^19)F nuclei. A number of experimental techniques are employed to verify solution-state and solid-state spectral assignments, and spectral anomalies are discussed. Both proton-coupled and proton-decoupled (^19)F solid-state spectra, recorded using specially designed spectrometer hardware, are presented. The huge gain in resolution afforded by the implementation of proton decoupling allows static and MAS spectra to yield previously inaccessible information pertaining to various NMR parameters of the fluorine nuclei. Advantages of (^1)H→(^19)F cross-polarisation experiments over single-pulse experiments are explained and rotational resonance, dipolar dephasing, T(_1), measurement and spin-exchange experiments are presented from which information regarding phenomena such as spin diffusion and polymorphism is gleaned. The second part of the thesis focusses on the topic of residual dipolar coupling, the transfer of quadrupolar effects to spin-1/2 nuclei via dipolar coupling and/or anisotropy m indhect coupling. Unexpected, field-dependent, multiplicities for signals in spectra of spin-1/2 nuclei are observed, which can be used to evaluate certain fundamental NMR parameters including the quadrupolar coupling constant and, m favourable cases, anisotropy in indirect coupling. The phenomenon is comprehensively studied for the (^13)C, (^35,37)Cl and (^13)C, (^79,81)Br spin-pairs in a range of solid halogenated compounds. Coupling to more than one halogen nucleus and long- range (non-bonded) coupling are considered. First-order perturbation, inverse first- order and "exact" theories, that allow the multiplet line positions to be predicted, are introduced and their results are subsequently compared to the experimentally observed the positions. Rapid molecular motion is shown to negate the effects of residual dipolar coupling and the phenomenon is analysed with the aid of NQR measurements.
31
Currie, Graeme. "Negative Ion Chemistry of Boron and Carbon Compounds / by Graeme Currie." Title page, contents and abstract only, 1988. http://web4.library.adelaide.edu.au/theses/09PH/09phc9762.pdf.
Full text
32
Jayatissa, Kuruppu Lilanthi. "A Metal-Free Approach to Biaryl Compounds: Carbon-Carbon Bond Formation from Diaryliodonium Salts and Aryl Triolborates." PDXScholar, 2015. https://pdxscholar.library.pdx.edu/open_access_etds/2229.
Full textAbstract:
Biaryl moieties are important structural motifs in many industries, including pharmaceutical, agrochemical, energy and technology. The development of novel and efficient methods to synthesize these carbon-carbon bonds is at the forefront of synthetic methodology. Since Ullmann’s first report of stoichiometric Cu-mediated homo-coupling of aryl halides, there has been a dramatic evolution in transition metal catalyzed biaryl cross-coupling reactions.
Our work focuses on the discovery and development of an unprecedented reagent combination for metal-free cross-coupling. It is hypothesized that direct carbon-carbon bond formation occurs via a triaryl-λ3-iodane and that electrophile/nucleophile pairing is critical for success in the reaction. Proof-of-concept for this approach focused on the reaction between bromo 4-trifluoromethylphenyl (trimethoxybenzene)-λ3-iodane and potassium 3-fluorophenyltriolborate. The spectator ligand and counter ions are important parameters for both reactivity and selectivity of the aryl group transfer in this reaction. Moderate to good yields of biaryl products are obtained by this method. Experimental evidence supports the assertion of a metal-free cross-coupling reaction.
33
Mercanti, Elia. "Synthesis and dynamic study of atropisomeric compounds containing boron-carbon bond." Master's thesis, Alma Mater Studiorum - Università di Bologna, 2016. http://amslaurea.unibo.it/10067/.
Full textAbstract:
In this thesis we studied the stereodynamic behavior of 1,2-azaborines variously substituted on boron (7a, 7b, 13). Depending on the hindrance of the asymmetric aryl substituent the resulting conformations could be stereolabile or configurationally stable. Through dynamic NMR and lineshape simulation, the energy rotational barriers of the different conformers are obtained. When the barrier is higher than 22-23 kcal/mol stable atropisomers that are fisically separable could be obtained (case of compound 13) and the free activation energy barrier is determinable by kinetic analysis. Absolute configuration of two atropisomers were assigned by comparison between computational calculations and experimental ECD. Isosteric compound 21 is then synthesized in order to compare the rotational barrier around B-Caryl with the one around Cnaphth-Caryl bond.
34
Batlle, Vilanova Pau. "Bioelectrochemical transformation of carbon dioxide to target compounds through microbial electrosynthesis." Doctoral thesis, Universitat de Girona, 2016. http://hdl.handle.net/10803/399148.
Full textAbstract:
In 2015 the average concentration of CO2 in the atmosphere exceeded 400 ppm. Some technologies, including CO2 capture and storage, are palliative. However, the development of alternatives to burning of fossil fuels focuses on the base of the problem and proposes substantial changes in the energy model. This thesis proposes the use of bioelectrochemical systems to transform CO2 into valuable products. This process is known as microbial electrosynthesis, and is based on the use of bacteria able to use the electrode as an electron donor (biocathode) to drive CO2 reduction. The results show that the production of hydrogen as intermediate is key to allow further CO2 reduction. This thesis has proven methane production, and organic liquid compounds of two (acetic acid) and four (butyric acid) carbons. The results invite to continue investigating to exploit all the potential of BES and enable its industrial scalabilityEl 2015 la concentració mitjana de CO2 a l’atmosfera va superar per primera vegada les 400 ppm. Algunes tecnologies, com la captura i emmagatzematge de CO2, són pal·liatives. En canvi, el desenvolupament d’alternatives a la crema de combustibles fòssils van a l’arrel del problema i proposen canvis substancials en el model energètic. Aquesta tesi planteja l’ús dels sistemes bioelectroquímics per transformar el CO2 en productes amb valor afegit. Aquest procés es coneix com electrosíntesi microbiana, i es basa en la utilització de bacteris capaços d’utilitzar l’elèctrode com a donador d’electrons (biocàtode) per portar a terme la reducció de CO2. Els resultats demostren que la producció d’hidrogen com a compost intermedi es la clau per poder portar a terme la reducció de CO2. Aquesta tesi ha demostrat la producció de metà, i compostos líquids orgànics de dos (acid acètic) i quatre (acid butíric) carbonis. Els resultats esperonen a continuar investigant per aprofitar tot el potencial dels BES i fer possible la seva escalabilitat industrial
35
Ho, Ka Yee. "Nanostructured environmental catalysts for carbon monoxide and volatile organic compounds removal /." View abstract or full-text, 2006. http://library.ust.hk/cgi/db/thesis.pl?EVNG%202006%20HO.
Full text
36
Schiessling, Joachim. "Angle-Dependent Electron Spectroscopy Studies of C60 Compounds and Carbon Nanotubes." Doctoral thesis, Uppsala universitet, Fysiska institutionen, 2003. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-3595.
Full textAbstract:
Fullerenes have been shown to constitute a prototypical building block for truly nanometer-sized devices and exotic nanounit-based materials, e.g., high-temperature superconductors. This makes the detailed understanding of fullerene electronic states in compounds and at interfaces of primary importance, since the high symmetry of the molecule greatly simplifies the starting point of the analysis. Carbon nanotubes, which combine one macroscopic with two nanoscopic dimensions, are perhaps of even greater practical interest. Angle-dependent electron spectroscopies have been employed in the present work to study these materials, characterizing their structure, bonding, and electronic states. For solid C60, the photoelectron angular distribution has been found to be essentially that of the free molecule, modified by solid state scattering; a similar distribution is found for K3C60. The surface and bulk electronic structure of K3C60 has been identified by angle-dependent core and valence photoelectron spectroscopy (PES) and x-ray emission spectroscopy. An insulating surface layer has been identified for this high-temperature superconductor. Angle-dependent valence PES is used to investigate the electronic states of C60/Al(110). Electron correlations are found to be the origin of the splitting observed in the molecular orbitals, which is quite sensitive to the molecular orientation. The components of the highest occupied molecular orbital are differentiated according to their overlap with the substrate. A rigid shift of valence- and core-levels has been observed even for ionic and covalent C60 compounds, reflecting the efficient static polarizability screening of the molecule. The alignment of multi-walled carbon nanotubes has been investigated by x-ray absorption spectroscopy, using the spectral intensity ratio of π*- and *-resonances. Core level combined with valence PES shows that the degree of defect structure varies from position to position on the sample. Valence photoelectron spectra of defect-free sample spots closely resembles the total DOS of graphite.
37
Wu, Jufang. "Modeling adsorption of organic compounds on activated carbon : A multivariate approach." Doctoral thesis, Umeå : Univ, 2004. http://urn.kb.se/resolve?urn=urn:nbn:se:umu:diva-297.
Full text
38
Zhang, Ruoxin. "Toward the synthesis of polycyclic aromatic compounds as nano-carbon cages." Morgantown, W. Va. : [West Virginia University Libraries], 2008. https://eidr.wvu.edu/etd/documentdata.eTD?documentid=5617.
Full textAbstract:
Thesis (M.S.)--West Virginia University, 2008.Title from document title page. Document formatted into pages; contains vii, 45 p. : ill. Includes abstract. Includes bibliographical references (p. 24-26).
39
Mizuhata, Yoshiyuki. "Syntheses and properties of kinetically stabilized tin-carbon double-bond compounds." 京都大学 (Kyoto University), 2006. http://hdl.handle.net/2433/73209.
Full text
40
Song, Li. "Liquid Phase Carbon-Thirteen Dynamic Nuclear Polarization Study of Monosubstituted Aromatic Compounds." Thesis, Virginia Tech, 1997. http://hdl.handle.net/10919/36999.
Full textAbstract:
In this work, liquid phase Carbon-thirteen DNP experimental data were collected in a flow transfer system for different mono-substituted aromatic compounds, such as, anisole, nitrobenzene and halobenzenes. These substitute groups covered a wide range of electronic effects from strong electron donating groups to strong electron withdrawing groups.
Hammett linear free energy relationship was used to quantitatively study the electronic effect of substituent on the carbon-thirteen DNP enhancement. It was found that the carbon-thirteen DNP enhancements at meta and para positions exhibits a reasonable correlation. A better correlation of carbon-thirteen DNP enhancements with the Hammett inductive factor was observed.
A large scalar dominated enhancement at ipso (C-1) position was observed for iodobenzene. This suggests that facile transfer of spin polarization to the C-1 carbon via the highly polarizable iodine atom is possible and the dominate electron transfer mechanism for this system.
A model of polarization transfer via spin diffusion of abundant proton spins was examined. The results indicate that it is not important.Master of Science
41
Zhu, Shuguang. "Generation of 1,3-dipoles containing carbon, nitrogen, sulphur and phosphorus." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1997. http://www.collectionscanada.ca/obj/s4/f2/dsk2/tape16/PQDD_0008/NQ34250.pdf.
Full text
42
Man, Wai Fan. "Fluorinated diamond-like carbon films deposited by ion beam CVD." HKBU Institutional Repository, 1999. http://repository.hkbu.edu.hk/etd_ra/192.
Full text
43
Lee, Ching Shya. "Study of glycerol electrochemical conversion into addes-value compounds." Thesis, Toulouse, INPT, 2016. http://www.theses.fr/2016INPT0076/document.
Full textAbstract:
Au cours des dernières années, la production excédentaire et sans cesse croissante de bioglycérol a provoqué une chute spectaculaire de son prix. Au cours des dernières années, un grand nombre de processus chimiques et biologiques ont été élaborés pour transformer le bioglycérol en divers produits à haute valeur ajoutée, tels que la dihydroxyacétone, l'acide glycolique, le 1,3-propanediol (1,3-PDO), 1,2-propanediol (1,2-PDO), l'acide glycérique, l'acide lactique, le carbonate de glycérol etc. Malheureusement, ces procédés souffrent de nombreux inconvénients comme par exemple, un coût élevé de production. Par conséquent, dans cette étude, une synthèse simple et robuste, basée sur un processus électrochimique a été introduite afin de convertir le bioglycérol en une grande variété de composés à haute valeur ajoutée. Cette étude rapporte pour la première fois l'utilisation de la résine Amberlyst-15 comme milieu réactionnel et comme catalyseur d'oxydo-réduction pour la conversion électrochimique du glycérol. La performance électrochimique du système composé par la résine Amberlyst-15 et l’électrode au platine (Pt), a été comparée à celle utilisant un milieu électrolytique conventionnel acide (H2SO4) ou alcalin (NaOH). D'autres paramètres tels que la température de réaction (température ambiante à 80 °C) et l’intensité du courant appliqué (1,0 A à 3,0 A) ont également été examinés. Dans les conditions expérimentales optimales, ce nouveau procédé électrocatalytique permet de convertir le glycérol, soit en acide glycolique, avec un rendement de 45% et une sélectivité élevée de 65%, soit en acide glycérique, avec un rendement de 27% et une sélectivité de 38%. D’autre part, deux autres électrodes ont été préparées et testées dans la réaction de transformation du glycérol : une électrode au charbon actif (ACC) et une électrode composite au noir de carbone et diamant CBD). A notre connaissance, il n’existe pas dans la littérature d’étude de transformation électrochimique du glycérol utilisant ce type d’électrodes. Dans ce travail, nous avons montré que le glycérol peut être oxydé en divers composés d’oxydation mais peut également être réduit avec succès en acide lactique,1,2-PDO et 1,3-PDO. Trois paramètres de fonctionnement, tels que la quantité de catalyseur (6.4 -12.8% w/v), la température de réaction [température ambiante (27°C) à 80 °C] et l’intensité du courant appliqué (1,0 A à 3,0 A), ont été testés. L'étude a révélé que, pour une quantité de catalyseur 9.6% w/v Amberlyst-15, un courant de 2,0 A et une température de 80 °C, la sélectivité en acide glycolique peut atteindre jusqu'à 72% et 68% (avec un rendement de 66% et 58%) en utilisant respectivement l’électrode ACC et l’électrode CBD. L'acide lactique a aussi été obtenu avec une sélectivité de 16% et un rendement de 15% en utilisant l’électrode ACC et une sélectivité de 27% pour un rendement de 21% dans le cas de l'électrode CBD. Enfin, l'électrooxydation et l'électro-réduction du glycérol a été effectuée dans une cellule à deux compartiments séparés par une membrane échangeuse de cations (Nafion 117). L’étude s’est focalisée sur l’électro-réduction. Trois cathodes (Pt, ACC et CDB) ont été évaluées dans les conditions suivantes : 2.0 A, 80 °C et 9.6% w/v Amberlyst-15. Les trois électrodes ont permis de réduire le glycérol en 1,2-PDO. Nous avons obtenu une sélectivité de 61% avec l’électrode au Pt et une sélectivité de 68% avec L’électrode CBD. En fait, c’est l’électrode ACC qui a démontré les meilleures performances puisqu’elle a permis de réduire le glycérol en 1,2-PDO avec une sélectivité élevée de 85%. Enfin, la réaction conduit aussi à la formation d’acétol et de diéthylèneglycol. Les mécanismes de formation des différents produits obtenus à partir de chaque réaction sont proposésThe price of crude glycerol has significantly decreased worldwide because of its oversupply. Many chemical and biological processes have been proposed to transform glycerol into numerous value-added products, such as glycolic acid, 1,3-propanediol (1,3-PDO), 1,2-propanediol (1,2-PDO), glyceric acid, and lactic acid. However, these processes suffer from several drawbacks, including high production cost. Therefore, in this study, a simple and robust electrochemical synthesiswas developed to convert glycerol into various value-added compounds. This study reports for the first time the use of Amberlyst-15 as a reaction mediumand redox catalyst for electrochemical conversion of glycerol. In the first part, the electrochemical performance of Amberlyst-15 over platinum (Pt)electrode was compared with that of conventional acidic (H2SO4) and alkaline (NaOH) media. Other parameters such as reaction temperature [room temperature (27°C) to 80 °C] and applied current (1.0 A to 3.0 A) were also examined. Under the optimized experimental condition, this novel electrocatalytic method successfully converted glycerol into glycolic acid after 8 h of electrolysis, with a yield of 45% and selectivity of 65%, as well as to glyceric acid after 3 h of electrolysis, with a yield of 27% and selectivity of 38%. In the second part of this study, two types of cathode electrodes, namely, activated carbon composite(ACC) and carbon black diamond (CBD) electrodes, were used in electrochemical conversion of glycerol. To the best of our knowledge, electrochemical studies of glycerol conversion using these electrodes have not been reported yet. Glycerol was also successfully reduced to lactic acid, 1,2-PDO, and 1,3-PDO, in addition to oxidation compounds (e.g. glycolic acid). Three operating parameters, namely, catalyst amount (6.4% to 12.8% w/v), reaction temperature [room temperature (27 °C) to 80 °C], and applied current (1.0 A to 3.0 A), were tested. In the presence of 9.6% w/v Amberlyst-15 at 2.0 A and 80 °C, the selectivity of glycolic acid can reach 72% and 68% (with yield of 66% and 58%) for ACC and CBD electrodes, respectively. Lactic acid was obtained as the second largest compound, withselectivity of 16% and yield of 15% for the ACC electrode and 27% selectivity and 21% yield for the CBD electrode. Finally, electro-oxidation and electroreduction of glycerol were performed in a two-compartment cell separated by a cation exchange membrane (Nafion 117). This study only focused on the electroreduction region. Three cathode electrodes (Pt, ACC, and CBD) were evaluated under the following conditions: 2.0 A, 80 °C, and 9.6% w/v Amberlyst-15. ACC demonstrated excellent performance in the electroreduction study and successfully reduced glycerol to 1,2-PDO, with a high selectivity of 85%. The selectivity of 1,2-PDO on Pt and CBD was 61% and 68%, respectively. Acetol and diethylene glycol were also obtained. The reaction mechanisms underlying the formation of these products are then proposed
44
Summers, Jack S. "Reactions of macrocyclic legand complexes of low valent nickel and cobalt with carbon dioxide : the preparation, characterization, and reactivity of a novel carbon dioxide adduct of cobalt." Diss., Georgia Institute of Technology, 1989. http://hdl.handle.net/1853/27283.
Full text
45
Zêzere, Bruno Miguel Martins. "Diffusivities of bioactive compounds in supercritical mixtures and expanded solvents." Master's thesis, Universidade de Aveiro, 2017. http://hdl.handle.net/10773/22524.
Full textAbstract:
Mestrado em Engenharia QuímicaNas últimas décadas, os fluidos supercríticos têm ganho maior destaque no âmbito dos paradigmas de biorrefinaria e sustentabilidade de processos químicos, surgindo como alternativa verde a muitos solventes orgânicos. Em particular, sendo o dióxido de carbono supercrítico (SC-CO2) o solvente preferido, são necessários valores experimentais e modelos preditivos de difusividades de solutos tanto em SC-CO2 puro como modificado com cossolvente. Esta tese surge como resposta à falta de dados e modelos nesta área, tendo como principal objetivo a medição e posterior modelação dos coeficientes de difusão de eucaliptol em SC-CO2 modificado com 8 % (m/m) de etanol e ainda etanol líquido puro. Recorrendo ao método cromatográfico de abertura de pico (CPB), procedeu-se à medição de difusividades do eucaliptol a diluição infinita (D12), numa gama de temperaturas entre 303.15 K e 333.15 K. Para a mistura SC-CO2 com etanol, a pressões de 150 a 275 bar, obtiveram-se valores compreendidos entre 0.547×10-4 a 1.042×10-4 cm2 s-1. Já em etanol puro, variando a pressão entre 1 e 100 bar, obtiveram-se difusividades entre 0.912×10-5 e 1.578×10-5 cm2 s-1. Os resultados de D12 foram analisados em função da temperatura, pressão, densidade e em coordenadas de Stokes-Einstein. Testou-se também uma série de modelos baseados nas teorias hidrodinâmica e de volume livre, bem como equações empíricas. Os valores calculados e experimentais foram comparados com base no desvio relativo absoluto médio (AARD). Para ambos os sistemas, destacam-se o modelo de dois parâmetros de Dymond-Hildebrand-Batschinski (DHB), o modelo Tracer Liu-Silva-Macedo com um parâmetro (TLSMd), um modelo modificado Stokes-Einstein-1, e as relações empíricas de Magalhães et al. (AARD entre 1.2 e 7.0 %). Em relação ao sistema ternário (eucaliptol na mistura SC-CO2 com etanol) os modelos de Wilke-Chang, Lai-Tan e Vaz et al. (AARD de 8.00, 8.36 e 1.29 %, respetivamente) foram os melhores. Quanto ao sistema binário (eucaliptol em etanol líquido) destaca-se ainda o modelo de Tracer Liu-Silva-Macedo (TLSM) (AARD de 6.75 %). Sugerem-se ainda correções a dois modelos, nomeadamente, à extensão do modelo de Liu-Silva-Macedo para intradifusividades em mixturas Lennard-Jones multicomponente, usando as regras de mistura propostas por Merzliak e Pfenning (LSM-MP) para o sistema ternário, e ao modelo DHB para o sistema binário, tendo-se obtido AARDs de 1.55 % e 3.70 %, respetivamente. Finalmente, procedeu-se à modelação de uma base de dados contendo 1453 pontos experimentais de difusividades correspondentes a 132 sistemas ternários distintos. Esta modelação foi realizada utilizando o modelo LSM-MP, ao qual foi proposta uma correção com base na divisão dos dados em 2 grupos: sistemas líquidos e supercríticos (AARDs de 9.39 % e 9.11 %, respectivamente).
Supercritical fluids have gained great importance within the concepts of biorefinery and sustainability of chemical processes. They are considered a “greener” alternatives to a vast group of conventional organic solvents with supercritical carbon dioxide (SC-CO2) being the most preferred. Currently, experimental data and predictive models for diffusivity in SC-CO2 systems are scarce especially regarding SC-CO2 systems modified with a cosolvent. The main objective of this thesis was the experimental determination and modelling of tracer diffusion coefficients (D12) of eucalyptol in SC-CO2 expanded with 8 wt.% ethanol (ternary system) and in pure ethanol (binary system). Furthermore improve the D12 modelling in multicomponent mixtures. Eucalyptol diffusivities were measured by the chromatographic peak broadening technique (CPB) in the temperature range 303.15 to 333.15 K. For the ternary system the values ranged from 0.547×10-4 to 1.042×10-4 cm2·s-1 for pressures between 150–275 bar. For the binary system the values ranged from 0.912×10-5 to 1.578×10-5 cm2·s-1 for pressures between 1-100 bar. The dependency of D12 in terms of temperature, pressure, solvent density, and Strokes-Einstein coordinates were also examined. A series of models based on hydrodynamic and free volume theory and on empirical correlations were tested and compared using the average absolute relative error (AARD) for calculated and experimental values. For both systems, the best results were obtained with the two parameter Dymon-Hildebrand-Batschinski (DHB) model, with the one parameter Tracer Liu-Silva-Macedo (TLSMd) model, with the modified Stokes-Einstein-1 model, and with the Magalhães et al correlations (AARD between 1.2 and 7.0 %). For the ternary system the Wilke-Chang, Lai-Tan, and Vaz et al. models can also be highlighted (achieving AARD of 8.00, 8.36 and 1.29 % respectively). For the binary system the TLSM model achieves an error of 6.75 %. In addition, two corrections are presented to improve model fitting, namely for the extension of Liu-Silva-Macedo model to multicomponent LJ intradiffusivities using mixing rules of Merzliak and Pfenning (LSM-MP) applied to the ternary system and for the DHB model applied to the binary system (AARD of 1.55 % and 3.70 %, respectively). Finally a database containing 132 ternary systems with a total of 1453 experimental diffusivity values was utilized for modeling D12 values, on the basis of the LSM-MP model. The AARD results obtained by splitting the database into two groups, namely liquid and supercritical systems, were 9.39 and 9.11 % respectively.
46
Clark, Christopher H. "Characterization and investigation of molybdenum carbides on activated carbon as hydrogenation catalysts." Morgantown, W. Va. : [West Virginia University Libraries], 2005. https://eidr.wvu.edu/etd/documentdata.eTD?documentid=4281.
Full textAbstract:
Thesis (M.S.)--West Virginia University, 2005.Title from document title page. Document formatted into pages; contains viii, 76 p. : ill. (some col.). Includes abstract. Includes bibliographical references (p. 54-57).
47
Duffield, Gaynor Louise. "Some studies of the reactions of carbon nucleophiles with aromatic nitro compounds." Thesis, Durham University, 1996. http://etheses.dur.ac.uk/5191/.
Full textAbstract:
Some reactions of aromatic nitro-compounds with carbon nucleophiles have been investigated. The techniques used include NMR spectroscopy, UV-visible spectroscopy and stopped-flow spectrophotometry. The initial rapid reactions of carbanions derived from ring-substituted phenylacetonitriles with 1,3,5-trinitrobenzene yield σ-adducts. Carbanions were generated from the phenylacetonitriles by reaction with sodium methoxide in methanol. Values of the equilibrium constants for the deprotonation reaction were determined spectrophotometrically. Rate constants for the σ-adduct forming reactions were measured in methanol using the stopped-flow method. With increasing carbanion reactivity rate constants for the C-C bond forming reaction increase to a limit of circa 10(^9) dm(^3) mol(^-1) s(^-1) close to the diffusion limit. Data were also obtained for reaction of the carbanions with 4-nitrobenzofuroxan and with 4-nitrobenzofurazan.An interesting slower reaction was observed in the reaction of carbanions with 1,3,5- TNB, 4-nitrobenzofuroxan and 4-nitrobenzofurazan. This yields coloured products and the nature of the process has been investigated. Attempts have been made to isolate the σ-adducts formed from carbanions. The adduct formed from 1,3,5-trinitrobenzene and phenylacetonitrile in the presence of triethylamine has been produced in crystalline form. NMR measurements in situ have indicated the formation of adducts from 4-nitrobenzofuroxan and from 4-nitrobenzofiirazan with deuterated nitromethane in the presence of triethylamine.
48
Herrington, Thomas James. "The reactivity of hydrogen and carbon dioxide mediated by main group compounds." Thesis, Imperial College London, 2014. http://hdl.handle.net/10044/1/24584.
Full textAbstract:
The focus of this thesis has been the design and synthesis of new frustrated Lewis pair (FLP) systems which from structural modifications retain their ability to activate H2/CO2, while displaying differing reactivity modes. Chapter Two describes the first practical synthesis of tris[3,5-bis(trifluoromethyl)phenyl]borane (BArF18). Gutmann-Beckett Lewis acidity measurements reveal that this borane is a more powerful Lewis acid than B(C6F5)3, but it nevertheless is found to bind H2O much more reversibly than B(C6F5)3. The BArF18/2,2,6,6-tetramethylpiperidine (TMP) FLP provides a rare example of H2 activation in Et2O solvent, in which the borohydride salt has been structurally characterised by X-ray crystallography. A novel bridging borohydride [mu-H(BArF18)2]⁻ was revealed, which contrasts to the characteristic terminal borohydrides formed by other borane based mediated FLP systems. Chapter Three details the design of fluorinated trisalkylboranes including B[CH(C6F5)2]3 which has been synthesised for the first time. This borane has been structurally characterised using X-ray crystallography and displays hydrogen bonding interactions between the ortho fluorines on each aryl ring and the adjacent CH proton. Interestingly, and despite this borane showing no Lewis acidity using Gutmann-Beckett and Childs techniques, the B[CH(C6F5)2]3/TMP FLP provides a rare example of H2 activation in THF solvent. Chapter Four details the synthesis of two classical trialkylsilylium-phosphane adducts [R3Si-PtBu3]+[B(C6F5)4]⁻ [R = Et; R = iPr] derived from the sterically unencumbered silylium ions R3Si+ (R = Et, iPr). Both adducts are not found to dissociate at elevated temperature and are appreciably stable towards decomposition. Moreover, adduct formation does not impede archetypal FLP reactivity; admittance of H2 led to heterolysis at elevated temperatures (90-100 °C), while CO2 activation occurs under ambient conditions. The latent stability of the CO2 adducts has allowed for their crystallographic characterisation. Subsequently, the activation parameters for CO2 uptake were investigated and support computational calculations.
49
"Activation of carbon-carbon and carbon-silicon bonds of nitriles by rhodium porphyrin radical." 2002. http://library.cuhk.edu.hk/record=b5895985.
Full textAbstract:
by Fung Chun-wah.Thesis (M.Phil.)--Chinese University of Hong Kong, 2002.
Includes bibliographical references (leaves 117-119).
Abstracts in English and Chinese.
Table of Contents --- p.i
Acknowledgments --- p.v
Abbreviations --- p.vi
Abstract --- p.vii
Chapter PART I: --- ACTIVATION OF CARBON-CARBON BONDS OF NITRILES BY RHODIUM PORPHYRIN RADICAL
Chapter CHAPTER 1 --- General Introduction --- p.1
Chapter 1.1.1 --- Activation of Carbon-Carbon Bond (CCA) by Transitional Metals --- p.1
Chapter 1.1.1.1 --- Potential Application of C-C Bond Activation --- p.1
Chapter 1.1.1.1.1 --- Cracking --- p.1
Chapter 1.1.1.1.2 --- Depolymerization --- p.2
Chapter 1.1.1.2 --- Thermodynamic and Kinetic Considerations in CCA --- p.3
Chapter 1.1.1.3 --- C-C Bond Activation in Strained System --- p.3
Chapter 1.1.1.4 --- C-C Bond Activation facilitated by Aromatization --- p.7
Chapter 1.1.1.5 --- C-C Bond Activation of Carbonyl Compounds --- p.9
Chapter 1.1.1.6 --- C-C Bond Activation of the Nitriles --- p.13
Chapter 1.1.1.7 --- Selective C-C Bond Activation on a Multimetallic Site --- p.16
Chapter 1.1.1.8 --- Intramolecular sp2 -sp3 C-C Bond Activation in PCP System --- p.17
Chapter 1.1.1.9 --- CCA in N-Heterocyclic Carbene --- p.18
Chapter 1.1.1.10 --- CCA in Pt(0) complexes bearing Chelating P´ةN- and P´ةP- Ligands --- p.19
Chapter 1. 1.1.11 --- CCA of Alkyne via Hydroiminoacylation by Rh(I) Catalyst --- p.20
Chapter I. 1.1.12 --- CCA in Homoallylic Alcohol by β-Allyl Elimination --- p.21
Chapter I. 1.1.13 --- C-C Bond Activation by Metathesis of Alkanes --- p.23
Chapter I.1.2 --- Structural Features of Rhodium Porphyrins --- p.25
Chapter I.1.3 --- Objective of the Work --- p.27
Chapter CHAPTER 2 --- Carbon-Carbon Bond Activation (CCA) of Nitriles by Rhodium Porphyrin Radical --- p.28
Chapter I.2.1 --- Introduction --- p.28
Chapter I.2.1.1 --- CCA of Nitroxides by Rhodium(II) Porphyrin Radical Rh(por) --- p.28
Chapter I.2.2 --- CCA of Nitriles by Rh(tmp) Radical --- p.29
Chapter I.2.2.1 --- Synthesis of Rh(tmp)Me --- p.29
Chapter I.2.2.2 --- Synthesis of Rh(tmp) Radical --- p.30
Chapter I.2.2.3 --- Ligand effect on CCA --- p.31
Chapter I.2.2.3.1 --- Synthesis of Phosphines --- p.31
Chapter I.2.2.3.2 --- Reactions between Rh(tmp) and Phosphines --- p.32
Chapter I.2.2.3.3 --- Synthesis of Alkyl Rh(tmp) --- p.35
Chapter I.2.2.4 --- CCA of Nitriles by Rh(tmp) with PPh3 added --- p.36
Chapter I.2.2.4.1 --- Synthesis of Nitrile --- p.36
Chapter I.2.2.4.2 --- Reactions between Rh(tmp) and Nitriles --- p.37
Chapter I.2.3.4 --- Proposed Mechanism of CCA --- p.44
Chapter CHAPTER 3 --- Experimental Section --- p.46
Conclusion --- p.63
References --- p.64
Chapter PART II --- ACTIVATION OF CARBON-SILICON BONDS OF NITRILES BY RHODIUM PORPHYRIN RADICAL --- p.71
Chapter CHAPTER 1 --- General Introduction --- p.71
Chapter II. 1.1 --- Carbon-Silicon Bond Activation by Transitional Metals --- p.71
Chapter II. 1.1.1 --- Potential Application of C-Si Bond Activation --- p.72
Chapter II.l. l.2 --- C(sp3)-Si Bond Activation --- p.73
Chapter II. 1.1.2.1 --- Intermolecular C(sp3)-Si Bond Activation in Strained System --- p.73
Chapter II. 1.1.2.2 --- Intermolecular C(sp3)-Si Bond Activation in Unstrained System --- p.76
Chapter II. 1.1.3 --- C(sp2)-Si Bond Activation --- p.78
Chapter II. 1.1.3.1 --- Intermolecular C(aryl)-Si Bond Activation --- p.78
Chapter II. 1.1.3.2 --- Intramolecular C(aryl)-Si Bond Activation --- p.84
Chapter II. 1.1.3.3 --- C(vinyl)-Si Bond Activation --- p.87
Chapter II. 1.1.4 --- C(sp)-Si Bond Activation --- p.89
Chapter II. 1.2 --- Objective of the Work --- p.92
Chapter CHAPTER 2 --- Carbon-Silicon Bond Activation (CSA) of Nitriles --- p.93
Chapter II.2.1 --- Introduction --- p.93
Chapter II.2.2 --- Reactions between Rh(tmp) Radical and Silylnitriles --- p.93
Chapter II.2.2.1 --- Investigation the CSA of Trimethylsilylcyanide by Rh(tmp) --- p.93
Chapter II.2.2.1.1 --- Synthesis of Rh(tmp)SiMe3 --- p.93
Chapter II.2.2.1.2 --- Synthesis of Rh(tmp)CN --- p.94
Chapter II.2.2.1.3 --- Reactions between Rh(tmp) and Trimethylsilylcyanide --- p.95
Chapter II.2.2.1.4 --- Ligands effect on CSA of Trimethylsilylcyanide by Rh(tmp) --- p.98
Chapter II.2.2.1.5 --- Temperature effect on CSA --- p.101
Chapter II.2.2.2 --- Reactions between Rh(tmp) and other Silylnitriles --- p.102
Chapter II.2.3 --- Mechanism of CSA of Trimethylsilylcyanide --- p.103
Chapter II.2.3.1 --- Proposed Mechanism of CSA of Trimethylsilylcyanide by Rh(tmp) --- p.104
Chapter II.2.4 --- A Comparison of CSA and CCA of Nitriles --- p.105
Chapter CHAPTER 3 --- Experimental Section --- p.107
Conclusion --- p.116
References --- p.117
List of Spectra --- p.120
Spectra --- p.121
50
"Carbon-hydrogen bond and carbon-carbon bond activation of alkanes with rhodium porphyrins." Thesis, 2010. http://library.cuhk.edu.hk/record=b6075086.
Full textAbstract:
Base-promoted CHA of unstrained alkanes with 5,10,15,20-tetratolylporphyrinatorhodium complexes, Rh(ttp)X (X = Cl, H, Rh(ttp)), has been achieved. Rh(ttp)Cl, reacted with n-pentane, n-hexane, n-heptane, c-pentane and c-hexane in the presence of potassium carbonate at 120 °C in 6 to 24 h to give rhodium porphyrin alkyls, Rh(ttp)R, in 29--76% yields. Mechanistic investigations suggested that Rh 2(ttp)2 and Rh(ttp)H are key intermediates for the parallel CHA step. The roles of base are (i) to facilitate the formation of Rh(ttp)Y (Y- = OH-, KCO3 -), (ii) to enhance the CHA rate with alkane and generate Rh(ttp)H by a Rh(ttp)Y species which is more reactive than Rh(ttp)Cl, and (iii) to provide a parallel CHA pathway by Rh2(ttp)2.c-Octane reacted with Rh(ttp)Cl at 120 °C in 7.5 h in the presence of K2CO3 to yield Rh(ttp)( n-octyl) and Rh(ttp)H in 33% and 58% yields, respectively. Mechanistic investigations indicate that the CCA product is generated from the Rh II(ttp)-catalyzed 1,2-addition of c-octane with Rh(ttp)H. Reaction of c-octane and Rh(ttp)H/Rh2(ttp) 2 (10:1) selectively yielded Rh(ttp)(n-octyl) in 73% at 120 °C in 15 h. The catalyst RhII(ttp) radical cleaves the C-C bond of c-octane to form to a Rh(ttp)-alkyl radical, which then abstracts a hydrogen atom from Rh(ttp)H to generate the Rh(ttp)( n-octyl), and subsequently leading to regeneration of the Rh II(ttp) radical. (Abstract shortened by UMI.)
K2CO3-promoted CHA of the ring-strained cycloheptane with Rh(ttp)Cl at 120 °C in 6 h gave the CHA product Rh(ttp)( c-heptyl) and together with, unexpectedly, the CCA product Rh(ttp)Bn, in 30% and 24% yields, respectively. Mechanistic studies revealed that Rh(ttp)( c-heptyl) undergoes beta-hydride elimination in neutral condition or beta-proton elimination in basic condition followed by reprotonation to give rhodium(III) porphyrin hydride, Rh(ttp)H, and c-heptene. Successive base-promoted CHA of c-heptene with Rh(ttp)H, followed by beta-proton elimination, generates cycloheptatriene. The CHA of cycloheptatriene with Rh(ttp)H formed Rh(ttp)(c-heptatrienyl), which underwent rearrangement with carbon-carbon cleavage at 120 °C in 16 d to yield Rh(ttp)Bn in 96% yield.
The objectives of this research focus on the investigation of carbon-hydrogen bond activation (CHA) and carbon-carbon bond activation (CCA) of alkanes by rhodium porphyrin complexes as well as the mechanistic understanding.
Chan, Yun Wai.
Adviser: Kin Shing Chan.
Source: Dissertation Abstracts International, Volume: 73-02, Section: B, page: .
Thesis (Ph.D.)--Chinese University of Hong Kong, 2010.
Includes bibliographical references.
Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web.
Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [201-] System requirements: Adobe Acrobat Reader. Available via World Wide Web.
Abstract also in Chinese.