Dissertations / Theses on the topic 'Olefin reactions'
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Burger, Barbara J. Bercaw John E. "Olefin insertion and [beta]-elimination reactions of permethylniobocene olefin hydride and permethylscandocene alkyl complexes /." Diss., Pasadena, Calif. : California Institute of Technology, 1987. http://resolver.caltech.edu/CaltechETD:etd-01162008-111854.
Full textYu, Miao. "Stereoselective Olefin Metathesis Reactions for Natural Product Synthesis." Thesis, Boston College, 2014. http://hdl.handle.net/2345/3861.
Full textChapter 1. The first examples of highly Z- and enantioselective ring-opening/cross-metathesis reactions are disclosed. Transformations involve meso cyclic olefin substrate and styrenes or enol ethers as olefin cross partners. A stereogenic-at-Mo monoaryloxide monopyrrolide (MAP) complex, prepared and used in situ, is discovered for the efficient formation of Z olefins. Such complex, bearing a relatively smaller adamantylimido and a larger chiral aryloxide ligand, leads to kinetic Z-selectivity due to the size differential. In most cases, the resulting disubstituted Z olefins are formed with excellent stereoselectivity (>95% Z). Chapter 2. The protocols for efficient Z-selective formation of macrocyclic disubstituted alkenes through catalytic ring-closing metathesis (RCM) is described. Stereoselective cyclizations are performed with either Mo- or W-based monoaryloxide monopyrrolide (MAP) complex at 22 oC. Synthetic utility of such broadly applicable transformation is demonstrated by synthesis of several macrocyclic natural products: relatively simpler molecules such as epilachnene (91% Z) and ambrettolide (91% Z), as well as advanced precursors to epothilones C and A (97% Z) and nakadomarin A (94% Z). Several principles of catalytic stereoselective olefin metathesis reactions are summarized based on the studies: 1) Mo-based catalysts are capable of delivering high activity but can be more prone to post-RCM isomerization. 2) W-based catalysts, though furnish lower activity, are less likely to cause the loss of kinetic Z selectivity by isomerization. 3) Reaction time is critical for retaining the stereoselectivity gained from kinetic, which not only applicable with MAP complexes but potentially with other complexes as well. 4) By using W-based catalyst, polycyclic alkenes can be accessed with sequential RCM reactions, without significant erosion of the existing Z olefins in the molecule. Chapter 3. An enantioselective total synthesis of anti-proliferative agent (+)-neopeltolide is presented. The total synthesis is accomplished in 11 steps for the longest linear sequence and 28 steps in total, including 8 catalytic reactions. Particularly, several Mo- or Ru-catalyzed stereoselective olefin metathesis reactions as well as N-hetereocyclic carbene (NHC)-catalyzed enantioselective boron conjugate addition to an acyclic enoate have proven to be effective for convergent construction of the molecule. The most important novelty of the study incorporates the explorations of feasibility of Z-selective cross-metathesis reactions to solve the challenge of installing two Z olefins with excellent selectivity
Thesis (PhD) — Boston College, 2014
Submitted to: Boston College. Graduate School of Arts and Sciences
Discipline: Chemistry
Sinha, Amritanshu. "Synthesis of molybdenum olefin metatheses catalysts through protonation reactions." Thesis, Massachusetts Institute of Technology, 2006. http://hdl.handle.net/1721.1/36262.
Full textVita.
Includes bibliographical references.
The attempted syntheses of molybdenum imido alkylidene complexes of the type Mo(NArc,)(CH-t-Bu)[Biphen] and Mo(N-2-CF3C6H4)(CHCMe2Ph)[Biphen] (Biphen2 = 3,3'-di-t-butyl-5,5',6,6'-tetramethyl- 1,1'-biphenyl-2,2'-diolate) from Mo(NArcl)(CH-t-Bu)(OTf)2(dme) and [Biphen]K2 have sporadically afforded mixtures containing the desired products along with the corresponding amido alkylidyne complexes, Mo(NHArcl)(C-t-Bu)[Biphen] and Mo(NH-2-CF3C6H4)(CCMe2Ph)[Biphen], respectively. The reaction of [Biphen]K2 with Mo(NArc,)(CH-t-Bu)(OTf)2(dme) and 10 equivalents of triethylamine reproducibly gave Mo(NHArc,)(C-t-Bu)[Biphen] in 40% yield. An X-ray crystal structure of a related complex, Mo(NHArc,)(CCMe2Ph)[S-Biphen] confirmed the proposed structure and also revealed that one ortho chloride approaches within 2.93 A of the metal approximately trans to the alkylidyne ligand. Attempts to prepare three other amido alkylidyne complexes in an analogous manner from Mo(NR")(CH-t-Bu)(OTf)2(dme) (NR" = N-2-CF3C6H4, N-2,6-i-Pr2C6H5, N-2,6-Me2C6H5) with [Biphen]K2 in the presence of 10-20 equivalents of triethylamine failed.
(cont.) Chapter 2 The reaction between Mo(NAr)(CH-t-Bu)(CH2-t-Bu)2 (Ar = 2,6-i-Pr2C6H3) and various alcohols (1-AdamantylOH, t-BuOH, ArOH, (CF3)2CHOH, (CF3)2MeCOH, (CF3)3COH, C6F5OH) in pentane or toluene yielded either complexes of the type Mo(NAr)(CH-t-Bu)(CH2-t-Bu)(OR) through direct addition of ROH across a Mo-C bond, or complexes of the type Mo(NAr)(CH2-t-Bu)3(OR) through direct addition of ROH across a Mo=C bond. The trineopentyl species appear to be formed when the alcohol has a relatively low pKa. The outcome also can depend upon whether the alcohol is employed neat, or in benzene, and mixtures are observed in some circumstances. The conversion of Mo(NAr)(CH2-t-Bu)3(OR) into Mo(NAr)(CH-t-Bu)(CH2-t-Bu)(OR) was shown to be unimolecular in several examples. Mo(NAr)(CH-t-Bu)(CH2-t-Bu)(OR) complexes have been found to be surprisingly active catalysts for various metathesis reactions. In contrast, M(NAr)(CH-t-Bu)(CH2-t-Bu)2 species are virtually inactive for metathesis. X-ray structures are reported for Mo(NAr)(CH2-t-Bu)3(OC6F5), Mo(NAr)(CH-t-Bu)(CH2-t-Bu)IOSi(O-t-Bu)3], [Mo(NAr)(CH-t-Bu)(CH2-t-Bu)(OC6F)12, and Mo(NAr)(CH-t-Bu)(CH2-t-Bu)(OC6F5)(PMe3).
(cont.) Chapter 3. Complexes of the type Mo(NR")(CHR')(N(R)3,5-C6H3Me2)2 (NR" = N-2,6-i-Pr2C6H, N-2,6-Me2C6Hs; R' = t-Bu, CMe2Ph; R' = i-Pr, t-Bu) and Mo(NR")(CHR')(NR2)2 (NR" = N-2,6-i-Pr2C6H,, N-2,6-Me2C6H5; R' = t-Bu, CMe2Ph; R = Me, Ph) can be isolated as orange-red solids in 30-35% yields or oils by reacting Mo(NR")(CHR')(OTf)2(dme) with LiN(R')(3,5-C6H3Me2)(ether) or with LiNR2. The synthesis of Mo(NR")(CHCMe2Ph)(NPh2)2 can be improved to 70-90% isolated yields when Mo(NR")(CHCMe2Ph)[OCMe(CF3)212 is used with LiNPh2(ether). Mo(NAr)(CHCMe2Ph)(NPh2)2 has been crystallographically characterized. Mo(NR")(CHR')(N(R)3,5-C6H3Me2)2 species reacted with t-BuOH and Me(CF3)2COH in benzene to give Mo(NR")(CHR')(OR)2 (OR = O-t-Bu, OCMe(CF3)2) in situ. However, no reactions of Mo(NR")(CHR')(N(R')3,5-C6H3Me2)2 were observed with enantiomerically pure diols such as [R-TRIP]H2 (3,3'-2,4,6-i-Pr3C6H2-binaphthol), [R-Ph]H2 (3,3'-C6H5-binaphthol), [rac-Mesitylbinap]H2 (3,3'-2,4,6-Me3C6H2-binaphthol) and [R-TMSbinapJH2 (3,3'-SiMe3-binaphthol).
(cont.) Bisamido complexes of the type Mo(NR")(CHR')(NPh2)2 were found to react with the aforementioned alcohols and diols to give Mo(NR")(CHR')(diolate) species in situ, which were further reacted in a catalytic fashion with two substrates to give the corresponding ring-closed products. Preliminary :results of the in situ catalysis demonstrated here compare fairly well with the analogous catalytic reactions reported with isolated catalysts. Appendix A. Mo(NAr)(CH-t-Bu)(CH2-t-Bu)(OC6F5) (Ar = 2,6-i-Pr2C6H3) can be reacted with 5-10 equivalents of trans-3-hexene to give a crystallographically characterized dimeric complex, [Mo(NAr)(CH2-t-Bu)(OC6F5)]2 that contains an unbridged Mo=Mo bond (2.410(8) A) in high yields. The above complex can also be prepared by treating Mo(NAr)(CH-t-Bu)(CH2-t-Bu)(OC6F5) with 0.5 equivalents of divinylbenzene. IMo(NAr)(CH2-t-Bu)(OC6F5)]2 will slowly catalyze the metathesis reactions of simple substrates, although less than 5% of the catalyst seems to be activated in such reactions.
(cont.) It was observed that catalytically active species for metathesis reactions can be generated by another Mo (d2) species, Mo(NArcl)(Biphen)(H2C=CH2)(ether) (NArc, = N-2,6-C12C6H3, Biphen2 = 3,3'-di-t-butyl-5,5',6,6'-tetramethyl-1,1'-biphenyl-2,2'-diolate) that could effect the ring-opening metathesis polymerization of norbornene. A mixture of Mo(NArcl)(Biphen)(H2C=CH2)(ether) and 20 equivalents of diallylether in benzene-d6 when treated with 10 equivalents of norbornene gives 54% conversion to dihydrofuran in 10 days.
by Amritanshu Sinha.
Ph.D.
Bowen, Lucy Elizabeth. "New reactions and activation methods in olefin trimerisation catalysis." Thesis, University of Bristol, 2008. http://hdl.handle.net/1983/7eba4c9b-e466-4390-8d24-f14002376be8.
Full textvan, Rooy Sara Emily. "Reactivity of rhodium-heteroatom bonds: from catalytic bond activation to new strategies for olefin functionalization." Thesis, University of British Columbia, 2007. http://hdl.handle.net/2429/444.
Full textPilyugina, Tatiana. "Molybdenum alkylidene complexes : syntheses and applications to olefin metathesis reactions." Thesis, Massachusetts Institute of Technology, 2007. http://hdl.handle.net/1721.1/40289.
Full textThis electronic version was submitted by the student author. The certified thesis is available in the Institute Archives and Special Collections.
Vita.
Includes bibliographical references.
Chapter 1. Alkylimido Molybdenum Complexes: Synthesis, Characterization and Activity as Chiral Olefin Metathesis Catalysts. Molybdenum olefin metathesis catalysts that contain previously unexplored aliphatic 1- phenylcyclohexylimido (PhCyN) and 2-phenyl-2-adamantylimido (PhAdN) groups were prepared and shown to be efficient and selective in a variety of olefin metathesis reactions. Five catalysts, Mo(NR)(CHCMe2Ph)[(S)-Biphen], Mo(NR)(CHCMe2Ph)[(R)-Trip](THF) (R = 1- adamantyl, PhCy, PhAd; Biphen = 3,3'-di-tert-butyl-5,5',6,6'-tetramethyl-1,1'-biphenyl-2,2'- diolate; Trip = 3,3'-bis(2,4,6-triisopropylphenyl)- 1,1'-binaphthyl-2,2'-diolate) and Mo(NAd)(CHCMe2Ph)[(R)-Trip](THF) (Ad = I-adamantyl), were synthesized. Their catalytic activity and enantioselectivity in desymmetrization reactions such as ring-closing metathesis of amines and lactams and ring-opening/cross metathesis of a substituted norborneol with styrene were compared to the results obtained with the only known alkylimido catalyst, Mo(NAd)(CHCMe2Ph)[(S)-Biphen]. The new catalysts prove to be similar to Mo(NAd)(CHCMe2Ph)[(S)-Biphen] in the majority of the studied reactions, and the examined catalysts show overall improvement in activity and enantioselectivity compared to the traditional arylimido catalysts. Chapter 2. Synthesis of Molybdenum Imido Alkyl and Alkylidene Complexes from Molybdenum Imido Tetrachlorides. Several new Mo(NR)C14(THF) species (R = C6F5, 3,5-(CF3)2C6H3, Ad, CPh3, and 2,6-i- Pr2C6H3) were prepared via the treatment of MoC14(THF)2 with azides, and then alkylated with neopentyl reagents. Addition of Mo(NR)C14(THF) complexes in toluene to a cold solution of NpMgCl in ether gave Mo(NR)Np3Cl species (R = CFs5, 3,5-(CF3)2C6H3, Ad, Ph3C, and 2,6-i- Pr2C6H3 (Ar); Np = CH2-t-Bu) in poor (35 %) to modest (51 %) yields. Heating Mo(NAr)Np3C1 in C6D6 to 50 OC results in a-hydrogen abstraction to give neopentane and a molecule whose
(cont.) Chapter 2. Synthesis of Molybdenum Imido Alkyl and Alkylidene Complexes from Molybdenum Imido Tetrachlorides. Several new Mo(NR)C14(THF) species (R = C6F5, 3,5-(CF3)2C6H3, Ad, CPh3, and 2,6-i- Pr2C6H3) were prepared via the treatment of MoC14(THF)2 with azides, and then alkylated with neopentyl reagents. Addition of Mo(NR)C14(THF) complexes in toluene to a cold solution of NpMgCl in ether gave Mo(NR)Np3Cl species (R = CFs5, 3,5-(CF3)2C6H3, Ad, Ph3C, and 2,6-i- Pr2C6H3 (Ar); Np = CH2-t-Bu) in poor (35 %) to modest (51 %) yields. Heating Mo(NAr)Np3C1 in C6D6 to 50 OC results in a-hydrogen abstraction to give neopentane and a molecule whose NMR spectra are consistent with it being Mo(NAr)(CH-t-Bu)NpCl; it decomposed bimolecularly upon attempted isolation. The other Mo(NR)Np3Cl species were found to be more stable than Mo(NAr)Np3C1, but when they did decompose at elevated temperatures, no neopentylidene complex could be observed. Addition of neopentyllithium to Mo(NR)Np3CI species (R = Ar, CPh3, or Ad) yielded Mo(NR)(CH-t-Bu)Np2 species, the adamantylimido version of which is unstable toward bimolecular decomposition. Addition of I equivalent of 2,6-diisopropylphenol, 2,6-dimethylphenol, or 3,5-(2,4,6-i-Pr3C6H2)2C6H30H (HIPTOH) to Mo(NCPh3)(CH-t-Bu)Np2 led to formation of Mo(NCPh3)(CH-t-Bu)Np(OR) species, while treatment of Mo(NCPh3)(CH-t- Bu)Np2 with C6FsOH gave Mo(NCPh3)Np3(OC6Fs). The three monophenoxide neopentylidene complexes showed metathesis activity for ring-closing a small selection of amines and an ether. X-ray studies were completed for Mo[N-3,5-(CF3)2C6H3]C14(THF), Mo[N-3,5-(CF3)2C6H3]Np3CI, Mo(NCPh3)Np3CI, and Mo(NCPh3)(CH-t-Bu)Np(OHIPT).
(cont.) Addition of I equivalent of 2,6-diisopropylphenol, 2,6-dimethylphenol, or 3,5-(2,4,6-i-Pr3C6H2)2C6H30H (HIPTOH) to Mo(NCPh3)(CH-t-Bu)Np2 led to formation of Mo(NCPh3)(CH-t-Bu)Np(OR) species, while treatment of Mo(NCPh3)(CH-t- Bu)Np2 with C6FsOH gave Mo(NCPh3)Np3(OC6Fs). The three monophenoxide neopentylidene complexes showed metathesis activity for ring-closing a small selection of amines and an ether. X-ray studies were completed for Mo[N-3,5-(CF3)2C6H3]C14(THF), Mo[N-3,5-(CF3)2C6H3]Np3CI, Mo(NCPh3)Np3CI, and Mo(NCPh3)(CH-t-Bu)Np(OHIPT).
(cont.) Chapter 3. Reactions of Mo Bispyrrolide Complexes with Enantiomerically Pure Diols: In Situ Catalyst Generation and Studies of Olefin Metathesis Reactions In the Fume Hood. Reactions of bispyrrolide molybdenum complexes Mo(NAd)(CHCMe2Ph)(pyr)2 and Mo(N-2-6-i-Pr2C6H3)(CHCMe2Ph)(pyr)2 with (R)-BiphenH2, and (R)-Benz2BitetH2 were examined (pyr = C4H4N, Benz2BitetH2 = 3,3'-dibenzhydryl-5,5',6,6',7,7',8,8'-octahydro-1,1'- binaphthyl-2,2'-diol). The resulting in situ generated catalysts were studied in three olefin metathesis reactions. These systems were found to be as active and enantioselective as the analogous isolated complexes. When the stock solutions of Mo(NAd)(CHCMe2Ph)(pyr)2, Mo(N- 2,6-i-Pr2C6H3)(CHCMe2Ph)(pyr)2, (R)-BiphenH2, and (R)-Benz2BitetH2 were stored in the fume hood over a period of one month, the in situ prepared catalysts were determined to be nearly identical in terms of their catalytic properties to the catalysts generated in situ in the glovebox.
by Tatiana Pilyugina.
Ph.D.
Mann, Tyler J. "Stereoselective Olefin Metathesis Reactions Catalyzed by Molybdenum Monoaryloxide Monopyrrolide Complexes." Thesis, Boston College, 2016. http://hdl.handle.net/2345/bc-ir:104995.
Full textChapter 1: Efficient Z-Selective Cross-Metathesis of Secondary Allylic Ethers Efficient Z-selective cross-metathesis of secondary allylic ethers were catalyzed by monoaryloxide monopyrrolide molybdenum complexes. Reactions involving both silyl and benzyl protected ethers were demonstrated, as well as ethers containing alkyl, aryl and alkynyl substituents. Mechanistic studies were performed, and the reactions were applied to the total synthesis of several ene-diyne natural products. Chapter 2. Stereoselective Total Synthesis of Disorazole C1 The stereoselective total synthesis of disorazole C1 is reported. The synthesis was completed in 12 longest linear steps. Our synthesis demonstrates the utility of Z-selective cross-metathesis to form both alkenyl borons and alkenyl halides. Another key transformation was a one-pot Suzuki-dimerization reaction to form a symmetric 30 membered ring in relatively high yield. Chapter 3. Stereoselective Cross-Metathesis to Form Trisubstituted Alkenes Initial studies into the stereoselective formation of trisubstituted olefins through molybdenum catalyzed cross-metathesis have been performed. Our mechanistic understanding of the reaction lead us to focus on the synthesis of alkenyl halides, which can be obtained in up 90% yield and 75:25 E:Z selectivity. Chapter 4: Ring-Closing Metathesis in the Synthesis of Natural Products Development of highly efficient and selective ring-closing metathesis reactions have enabled collaborators to successfully implement routes in total synthesis endeavors. A diastereoselective seven-membered ring-closing metathesis enabled the successful synthesis of (±)-tetrapetalone A methyl-aglycon. An enantioselective ring-closing metathesis to form a six membered ring has provided access to enantioenriched aspidosperma alkaloids
Thesis (PhD) — Boston College, 2016
Submitted to: Boston College. Graduate School of Arts and Sciences
Discipline: Chemistry
Brown, Gavin M. "Synthesis and screening of ligands for catalytic olefin oligomerisation reactions." Thesis, Loughborough University, 2009. https://dspace.lboro.ac.uk/2134/6275.
Full textFinnegan, David Francis. "Tandem Reactions Involving Ruthenium Alkylidenes." Thesis, Boston College, 2009. http://hdl.handle.net/2345/728.
Full textTandem Reactions have proven themselves to be useful reactions for the synthesis of highly complex materials. Ruthenium alkylidenes are shown to be useful precursors for the development of new tandem processes. First, a new tandem metathesis/hetero-Pauson-Khand process is developed using Grubbs' second generation catalyst. Next, various metatheis/olefin isomerization processes are explored
Thesis (PhD) — Boston College, 2009
Submitted to: Boston College. Graduate School of Arts and Sciences
Discipline: Chemistry
Lundin, Angelica. "Quantum chemical studies of olefin epoxidation and benzyne biradicals /." Göteborg, Sweden : Göteborg University, Faculty of Science, 2007. http://www.loc.gov/catdir/toc/fy0801/2007440811.html.
Full textHamidi, A. "Interaction between hindered piperidine light stabilisers and antioxidants in the thermal and photochemical oxidation of polyolefins." Thesis, Manchester Metropolitan University, 1987. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.378064.
Full textEwart, Sean William. "Synthesis, solution dynamics and olefin polymerization reactions of some monocyclopentadienyl titanium complexes." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1998. http://www.collectionscanada.ca/obj/s4/f2/dsk2/ftp02/NQ31925.pdf.
Full textLopez, Suarez Laura. "Tetra-substituted olefin synthesis using palladium-catalysed C-H activation." Thesis, University of Edinburgh, 2012. http://hdl.handle.net/1842/5869.
Full textHuang, Chung-Yang. "Development of Electron-Deficient Olefin Ligands for Nickel-Catalyzed Aziridine Cross-Coupling Reactions." Thesis, Princeton University, 2015. http://pqdtopen.proquest.com/#viewpdf?dispub=3729674.
Full textLigands play a vital role in transition metal catalysis: they modulate the steric and electronic properties of the metal catalysts, thus enabling the desired reactivity and selectivity. The dominant ligand classes include phosphines, amines, and NHCs, which render the metal centers more electron-rich through σ-donation. On the contrary, although the π-accepting, electron-deficient olefins (EDOs) are known to promote bond-forming reductive elimination, they have not been widely utilized as ligands for catalysis. Development of these EDOs into a modular class of ligands would allow for novel reactivity that cannot be achieved with existing ligand classes.
In an effort to develop cross couplings with non-traditional electrophiles, we discovered that an electron-deficient olefin, dimethylfumarate, is the optimal ligand for nickel-catalyzed Negishi alkylation of styrenyl aziridines. Mechanistic studies revealed a stereoablative mechanism of this reaction and that the sulfonamide group is involved in directing the C–C formation. Furthermore, the critical role of dimethylfumarate is most likely be promoting the reductive elimination.
To expand the substrate scope to the less activated alkyl aziridines, we designed an N-protecting group, cinsyl (Cn), which contains an electron-deficient olefin as the directing group. Effective arylations and alkylations of Cn-aziridines can be achieved utilizing the nickel catalyst and organozinc reagents. The stereoablative mechanism going through radical intermediates was again observed.
The modular framework of dimethylfumarate allows us to modify the ligand structure and achieve more challenging transformation. We found that an indenylsultam-derived ligand, Fro-DO, enables cross coupling with 1,1-disubstituted styrenyl aziridines to generate all-carbon quaternary centers. Solid-state analysis revealed a unique U-shape structure of this ligand, which may be responsible for the improved reactivity and selectivity. Additionally, utilization of a chiral camphorsultam-derived EDO ligand provided modest but promising enantioselectivity of this reaction.
In this thesis work, we have demonstrated that EDOs can be developed into a novel ligand class for transition metal catalysis. The structural platform allows for rapid ligand modification and reaction evaluation. We expect that future exploration of these EDO ligands will unlock new reactivity and selectivity that has not been possible with current technology.
Xu, Conghui. "Rhodium-mediated Activation and Borylation Reactions of Fluorinated Olefins." Doctoral thesis, Humboldt-Universität zu Berlin, 2020. http://dx.doi.org/10.18452/22174.
Full textThe dissertation reports on studies on the reactivity of rhodium complexes towards different fluorinated olefins with a focus on C–F activation steps and borylation reactions. The rhodium(I) hydrido complex [Rh(H)(PEt3)3] (1) was employed as catalyst in the reactions of HFO-1234yf, HFO-1234ze, HFO-1225zc and HFO-1225ye with HBpin. A product mixture consisting of borylation products was obtained. Selective mono and dihydroboration reactions of 3,3,3-trifluoropropyne were achieved by employing complex 1 as the catalyst. Similarly, trifluoroethylene was also converted into a mixture of products by the reaction with HBpin with complex 1 as the catalyst. A stoichiometric reaction of complex 1 resulted in the C–F bond activation as well as a coordination of trifluoroethylene to give complex trans-[Rh(F)(ƞ2-CF2CFH)(PEt3)2]. Furthermore, the C–F bond activation was also realized with complex 1 and 1,1,2-trifluorobutene. Mechanistic investigations of the reaction of complex 1 towards 1,1,2-trifluorobutene at variable temperatures indicated the formation of products of coordination, insertion of the olefin and subsequent β-H elimination, C–F oxidative addition as well as HF reductive elimination steps. Furthermore, when utilizing complex 1 or [Rh(Bpin)(PEt3)3] (3) as catalysts, stoichiometric and catalytic hydroboration reactions of pentafluorostyrene occurred with HBpin. The rhodium(I) complexes 1 and 3 were capable of the coordination of the olefin and a C–F bond activation reaction with pentafluorostyrene, while complex [Rh(Me)(PEt3)3] promoted the C–H bond activation. At 333 K, the activation of the fluorinated aromatic ring occurred at the 4-position, while at room temperature, an activation at the 2-position was preferred.
Gaide, Tom [Verfasser], Arno [Akademischer Betreuer] Behr, and Stefan [Gutachter] Mecking. "Sustainable process development for olefin carbonylation reactions / Tom Gaide ; Gutachter: Stefan Mecking ; Betreuer: Arno Behr." Dortmund : Universitätsbibliothek Dortmund, 2017. http://d-nb.info/1148746978/34.
Full textMarinescu, Smaranda Constanţa. "Molybdenum and tungsen alkylidene species for catalytic Enantio-, Z-, and E-selective olefin metathesis reactions." Thesis, Massachusetts Institute of Technology, 2011. http://hdl.handle.net/1721.1/65475.
Full textCataloged from PDF version of thesis.
Includes bibliographical references.
CHAPTER1 A general introduction to olefin metathesis is given. Highlights include a detailed discussion of group VI imido alkylidene catalysts. CHAPTER 2 Several bispyrrolide species Mo(NAr)(CHCMe 2Ph)(pyr)2 (Ar = 2,6-i-Pr2C6H3, pyr = 2,3,4,5- tetramethylpyrrolide, 2,5-diisopropylpyrrolide, or 2,5-diphenylpyrrolide) have been synthesized and characterized. X-ray structural studies of these species display one r 1-pyrrolide ring and one 5-p1y rrolide ring. Monohexafluoro-t-butoxide pyrrolide (MAP) species can be prepared, either through addition of one equiv of Me(CF 3)2COH to a bispyrrolide or through reactions between the lithium pyrrolide and the bishexafluoro-t-butoxide. Trimethylphosphine adducts of MAP hexafluoro-t-butoxide species, Mo(NAr)(CHCMe 2Ph)(pyr)[OC(CF 3)2Me](PMe3), have been prepared. An X-ray structural study of one of these phosphine adducts was found to have PMe3 bound approximately trans to the pyrrolide. This adduct serves as a model for the structure of the initial olefin adduct in olefin metathesis. CHAPTER 3 The two diastereomers of Mo(NAr)(CHCMe2Ph)(2,5-dimethylpyrrolide)(OBitet) ((SMRJ)-1 and (RMR])-1, respectively, where OBitet is an enantiomerically pure (R) phenoxide and Ar = 2,6- diisopropylphenyl), form adducts with PMe3. One of these ((RmR)-1(PMe3)) has been isolated. An X-ray structure reveals that PMe3 has added trans to the pyrrolide; it is a model for where an olefin would attack the metal. Trimethylphosphine will catalyze slow interconversion of (SMRI)- 1 and (RMRJ)-1 via formation of weak PMe3 adducts, which undergo a series of Berry pseudorotations or (equivalent) turnstile rearrangements. The interconversion of diastereomers in the presence of trimethylphosphine was investigated by a variety of kinetic studies, variable temperature NMR spectroscopic studies, and labeling studies. CHAPTER 4 Addition of ethylene to Mo(NAr)(CHCMe 2Ph)(OBitet)(2,5-Me2Pyr) led to the trigonal bipyramidal metallacyclobutane complex, Mo(NAr)(C 3H6)(OBitet)(2,5-Me 2Pyr), in which the imido and aryloxide ligands occupy axial positions. NMR studies of Mo(NAr)(C 3H6)(OBitet)(2,5-Me 2Pyr) showed that the metallacyclobutane - species is in equilibrium with ethylene/methylidene intermediates before losing ethylene to yield the respective methylidene complexes. Detailed NMR studies of Mo(NAr)(C3H6)(OBitet)(Me 2Pyr) were carried out and compared with previous studies of W(NAr)(C 3H6)(OBitet)(Me 2Pyr). .It could be shown that Mo(NAr)(C 3H6)(OBitet)(Me 2Pyr) forms an ethylene/methylidene intermediate at 20 0C at a rate that is 4500 times faster than the rate at which W(NAr)(C 3H6)(OBitet)(Me 2Pyr) forms an ethylene/methylidene intermediate. It is proposed that the stability of methylidene complexes coupled with their high reactivity account for the high efficiency of many olefin metathesis processes that employ MonoAryloxidePyrrolide (MAP) catalysts. CHAPTER 5 MonoAryloxide-Pyrrolide (MAP) olefin metathesis catalysts of molybdenum that contain a chiral bitetralin-based aryloxide ligand are efficient for ethenolysis of methyl oleate, cyclooctene, and cyclopentene. Ethenolysis of 5000 equivalents of methyl oleate produced 1- decene (1D) and methyl-9-decenoate (M9D) with a selectivity of >99%, yields up to 95%, and a TON (turnover number) of 4750 in 15 hours. Tungstacyclobutane catalysts gave yields approximately half those of molybdenum catalysts, either at room temperature or at 50 0C, although selectivity was still >99%. Ethenolysis of 30000 equiv of cyclooctene to 1,9-decadiene could be carried out with a TON of 22500 at 20 atm (75% yield), while ethenolysis of 10000 equiv of cyclopentene to 1,6-heptadiene could be carried out with a TON of 5800 at 20 atm (58% yield). Some MonoAryloxide-Pyrrolide (MAP) olefin metathesis catalysts of molybdenum that are Z selective for the homocoupling of terminal olefins can be employed for the selective ethenolysis of Z internal olefins in the presence of E internal olefins in minutes at 22 0C. Therefore it is possible to take an E:Z mixture to a pure E product by selectively destroying the Z component and removing the resulting low molecular weight ethenolysis products. Exclusively E olefins can be obtained from terminal olefins in a two step process: the first step consists of a nonselective homocoupling to give approximately a 4:1 E:Z; while the second step consists of Zselective ethenolysis of the olefinic mixture to generate pure E-olefin. Several functional groups can be tolerated, such as ethers and esters. CHAPTER 6 3,5-Dimethylphenylimido complexes of tungsten can be prepared using procedures analogous to those employed for other tungsten catalysts, as can bispyrrolide species, and MonoAryloxide- Pyrrolide (MAP) species. X-ray structural studies of metallacylcobutane MAP species show them to have the expected TBP geometry with the imido and aryloxide ligands in apical positions. Homocoupling of 1-hexene, 1-octene, and methyl-10-undecenoate are achieved in 45- 89% yield and a Z-selectivity of >99% with W(NAr")(C 3H6)(pyr)(OHIPT) (Ar" = 3,5-Me 2C6H3; HIPT = 2,6-(2,4,6-(i-Pr) 3C6H2)2C6H3) as a catalyst. Homocoupling of terminal olefins in the presence of E olefins elsewhere in the molecule was achieved with excellent selectivity. CHAPTER 7 A monotriflate species, Mo(NAd)(CHCMe 2Ph)(OHIPT)(OTt) (Ad = 1-Adamantyl), is obtained by salt metathesis of bistriflate species and one equivalent of lithium alkoxide. Addition of PMe3 to the monotriflate species led to the formation of a phosphine adduct. An X-ray structural study revealed a square pyramidal coordination environment, with the alkylidene in the apical position and the phophine trans to the triflate ligand. The triflate can be exchanged with a variety of anionic ligands, such as 2-Mespyrrolide and t-butoxide. These species have been characterized by X-ray crystallography and they reveal the expected tetrahedral geometry. CHAPTER 8 Exposure of diethylether solution of Mo(NAr)(CHCMe 2Ph)(Me2Pyr)(OSiPh3) (1) to one atmosphere of ethylene for one hour led to the formation of the ethylene complex Mo(NAr)(CH 2CH 2)(Me 2Pyr)(OSiPh 3) (2). Addition of one equivalent of triphenylsilanol to a solution of 2 gives Mo(NAr)(CH 2CH2)(OSiPh 3)2 (3) readily. Mo(NAr)(CHCMe 2Ph)(OTf)2(dme) reacts slowly with ethylene (60 psi) in toluene at 80 'C to give cis and trans isomers of Mo(NAr)(CH 2CH 2)(OTf)2(dme) (4a) in the ratio of -2(cis):1. Addition of lithium 2,5- dimethylpyrrolide to 4a under 1 atm of ethylene produces Mo(NAr)(CH 2CH 2)(h-Me2Pyr)(h 5- Me2Pyr) (5). Neat styrene reacts with 2 and 3 to generate the styrene complexes, Mo(NAr)(CH 2CHPh)(Me2Pyr)(OSiPh 3) (6) and Mo(NAr)(CH 2CHPh)(OSiPh3)2 (7), respectively. Similarly, the trans-3-hexene complex, Mo(NAr)(trans-3-hexene)(OSiPh 3)2 (8a), can be prepared from 3 and neat trans-3-hexene. When 3 is exposed to 1 atm of ethylene, the molybdacyclopentane species, Mo(NAr)(C 4Hs)(OSiPh3)2 (9), is generated. X-ray structural studies were carried out on 2, 5, 7, 8a, and 9. All evidence suggests that alkene exchange at the Mo(IV) center is facile, followed by cis,trans isomerization and isomerization via double bond migration. In addition, trace amounts of alkylidene complexes are formed that result in slow metathesis reactions of free olefins to give (e.g.) a distribution of all possible linear olefins from an initial olefin and its double bond isomers. APPENDIX A Monopyrrolide monothiolate species of type Mo(NAr)(CHR)(2,5-Me 2NC4H2)(SR') (Ar = 2,6-i- Pr2C6H3; R = CMe3, CMe2Ph; R'= 2,6-Me 2C6H3, C6F5) have been synthesized by protonolysis of Mo(NAr)(CHR)(2,5-Me 2NC4H2)2 with one equivalent of R'SH. Addition of one equiv of 2,6- Me2C6H3SH to Mo(NAr)(CHCMe 2Ph)[OC(CF3)2Me] 2 led to the formation of Mo(NAr)(CHCMe 2Ph)(2,6-Me2C6H3S)[OCMe(CF 3)2] (3) in good yield. Using the same method, Mo(NAr)(CHCMe 3)(SCMe 3)[OC(CF 3)2Me] (4) was synthesized. A ligand scrambling effect was observed by 1H NMR spectroscopy leading to the formation of bisalkoxide and bisthiolate species. The bisalkoxide species, Mo(NAr)(CHCMe 2Ph)(OBitet) 2, was synthesized by salt metathesis of Mo(NAr)(CHCMe 2Ph)(OTf) 2(dme) and two equivalents of BitetONa. An X-ray structural study of this compound shows an anti configuration of the alkylidene.
by Smaranda Constanţa Marinescu.
Ph.D.
Meurs, Martin van. "Catalysed chain growth on zinc alkyls and chain trnsfer reactions in transition metal catalysed olefin polymerisation." Thesis, Imperial College London, 2005. http://hdl.handle.net/10044/1/8180.
Full textZheng, Feng. "Olefin oligomerization reactions theoretical studies using cyclometallated palladium(II) catalysts and experimental studies on platinum(II) analogues." Doctoral thesis, University of Cape Town, 2012. http://hdl.handle.net/11427/10908.
Full textIncludes bibliographical references.
Ethylene oligomerization reactions catalysed by cyclometallated palladium(II) N-benzylidenebenzylamine complexes were studied theoretically. Density functional theory (DFT) calculations are reported on the interaction of various MAO models with the methylated pre-catalyst. The neutral MAO dissociation process is shown to remain the major interaction that takes place in the Pd/MAO interactions. On the other hand, the formal methyl abstraction process could be also feasible if more energy is provided. Therefore, the relative energies were calculated for intermediates and transition states for both Cossee-type and metallacycle mechanisms.
Nawdiyal, Amruta [Verfasser], and Fabian [Gutachter] Mauß. "The influence of allylic site abstraction reactions of olefin on cyclo-paraffin formation / Amruta Nawdiyal ; Gutachter: Fabian Mauß." Cottbus : BTU Cottbus - Senftenberg, 2019. http://d-nb.info/1187741086/34.
Full textSchuehler, Sherwood Danielle E. "Olefin metathesis for metal incorporation and ligand exchange reactions for the preparation of new ruthenium compounds and materials." Related electronic resource: Current Research at SU : database of SU dissertations, recent titles available full text, 2009. http://wwwlib.umi.com/cr/syr/main.
Full textQuan, Xu. "Hydrogenation, Transfer Hydrogenation and Hydrogen Transfer Reactions Catalyzed by Iridium Complexes." Doctoral thesis, Stockholms universitet, Institutionen för organisk kemi, 2015. http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-119701.
Full textAt the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 5: Submitted. Paper 6: Manuscript.
Gülak, Samet [Verfasser]. "Olefin-Assisted Iron and Cobalt Catalyzed Cross-Coupling Reactions for the Synthesis of Highly Functionalized Styrene Derivatives / Samet Gülak." München : Verlag Dr. Hut, 2013. http://d-nb.info/1043892397/34.
Full textMugo, Jane Ngima. "Polymerization and oligomerization reactions mediated by metallodendrimers of zinc and palladium." Thesis, Stellenbosch : Stellenbosch University, 2012. http://hdl.handle.net/10019.1/20215.
Full textTrifonova, Anna. "Synthesis of Novel Chiral Bicyclic Ligands and their Application in Iridium-Catalyzed Reactions." Doctoral thesis, Uppsala : Acta Universitatis Upsaliensis, 2005. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-5783.
Full textFunk, Sebastian [Verfasser], Jürgen [Akademischer Betreuer] Schatz, Jürgen [Gutachter] Schatz, and Evgeny [Gutachter] Kataev. "Pillararenes as Supramolecular Additives in Suzuki Cross-Coupling and Olefin Metathesis Reactions in Water / Sebastian Funk ; Gutachter: Jürgen Schatz, Evgeny Kataev ; Betreuer: Jürgen Schatz." Erlangen : Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), 2020. http://d-nb.info/1221370359/34.
Full textWang, I.-Hsiung 1950. "Kinetics Studies of Substituted Tungsten Carbonyl Complexes." Thesis, University of North Texas, 1989. https://digital.library.unt.edu/ark:/67531/metadc330797/.
Full textGainsforth, Joanne L. "Forging a new chemical bond, theory and experiment studies of the metal-alkyne interaction in M(CO)[subscript]x([eta]²-alkyne) (M = Ru, Os, W) compounds and isotope effects in olefin addition reactions." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1998. http://www.collectionscanada.ca/obj/s4/f2/dsk2/ftp01/MQ34364.pdf.
Full textAmyes, T. L. "Mechanisms of carboxyl-activated elimination reactions." Thesis, University of Cambridge, 1986. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.383698.
Full textFlower, Stephen. "Lewis acid mediated reactions of olefins with carbonyls." Thesis, University of Bath, 2002. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.248114.
Full textMikus, Malte Sebastian. "Mechanistic Studies, Catalyst Development, and Reaction Design in Olefin Metathesis:." Thesis, Boston College, 2019. http://hdl.handle.net/2345/bc-ir:108382.
Full textChapter 1. Exploring Ligand Effects in Ruthenium Dithiolate Carbene Complexes. Ruthenium dithiolate metathesis catalysts discovered in the Hoveyda group have been a valuable addition to the field of olefin metathesis. While the catalyst shows unique selectivity and reactivity, quantifying and mapping key interactions in the catalyst framework to elucidate and explain causes is difficult. We, therefore, decided to use the neutral chelating or monodentate ligand, controlling initiation, as a structural probe. By altering its properties and observing changes in the catalyst, we sought to deepen our understanding of these complexes. We established a trans influence series with over 20 catalysts and correlated the impact on catalyst initiation. Further, we show that in the case of strongly σ-donating and π-accepting ligands such as phosphites and isonitriles, the complex exhibits fluxional behavior. The catalysts ground state is elevated to such a degree that thiolate Ruthenium bonds become labile and rapidly exchange. While Ruthenium dithiolate catalysts were readily applied to metathesis polymerization, their use in the synthesis of small molecules was initially less forthcoming. Specifically, reactions involving terminal olefins lead to rapid catalyst deactivation and only low conversion. We were able to determine that the potential energy stored in the trans-influence between the thiolate ligand and the NHC can be released in a sulfur shift to reactive Ruthenium methylidene species. Since methylidenes are formed by reaction with terminal olefins, use of an excess of internal olefins can prevent their formation. Chapter 2. Harnessing Catalyst Fluxionality in Olefin Metathesis. Depending on its use, material requirements can vary significantly. Materials that can easily be adapted to a given application, for example by varying tensile strength, melting point or solubility, are desirable. Controlling the polymers tacticity (the adjacent stereocenters in a polymer chain) is a straight forward way to achieve just that. Ru dithiolate catalysts should give highly syndiotactic polymers due to their single stereocenter undergoing inversion during every metathesis step. The fluxional nature of the catalyst allows for control of polymer tacticity from 50% (atactic) to ≥95% syndiotacticity by changing monomer concentration. We determined the factors which are responsible for fluxionality and synthesized complexes that give either high or low levels of tacticity over a broader range of monomer concentration. Chapter 3. Harnessing Catalyst Fluxionality in Olefin Metathesis. The importance of fluorine-containing molecules is hard to understate, keeping in mind the surge of new methodologies for their synthesis and the medical breakthroughs they enable. However, efficient and practical syntheses of stereodefined alkenyl fluorides are rare. In this context, we have developed enantioselective boryl allylic substitution of allylic fluorides, which yield enantioenriched γ-alkenyl fluoride substituted allyl boronate esters. The reaction is catalyzed by Cu-based catalysts that are prepared in-situ and delivered as products with high yield and enantioselectivity. Mechanistic inquiry shows the reaction is not a concerted allylic substitution. An intermediate Cu alkyl complex is formed after the Cu boron addition is made to the double bond, which only slowly undergoes β-fluorine elimination in the presence of a Lewis acid
Thesis (PhD) — Boston College, 2019
Submitted to: Boston College. Graduate School of Arts and Sciences
Discipline: Chemistry
Ho, Chun-yu. "Asymmetric epoxidation of olefins and cyclization reactions catalyzed by amines /." View the Table of Contents & Abstract, 2005. http://sunzi.lib.hku.hk/hkuto/record/B31490682.
Full textHo, Chun-yu, and 何振宇. "Asymmetric epoxidation of olefins and cyclization reactions catalyzed by amines." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2005. http://hub.hku.hk/bib/B45014814.
Full textCheck, Christopher. "Palladium-Catalyzed Inter- and Intramolecular Allylic Oxidation Reactions of Olefins." The Ohio State University, 2012. http://rave.ohiolink.edu/etdc/view?acc_num=osu1348618169.
Full textSpyropoulos, K. "Endocyclic electron-rich olefins : Their preparation, characterisation and some reactions." Thesis, University of Sussex, 1985. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.371203.
Full textRIGHETTINI, ROBIN FRANCIS. "SPONTANEOUS REACTIONS AND NEW COPOLYMERS FROM ELECTRON DEFICIENT, HIGHLY SUBSTITUTED OLEFINS." Diss., The University of Arizona, 1985. http://hdl.handle.net/10150/188094.
Full textXu, Conghui [Verfasser]. "Rhodium-mediated Activation and Borylation Reactions of Fluorinated Olefins / Conghui Xu." Berlin : Humboldt-Universität zu Berlin, 2020. http://d-nb.info/1222973480/34.
Full text焦關勝 and Guansheng Jiao. "Ketone catalyzed diastereoselective and enantioselective epoxidation of olefins: catalyst design and syntheticapplication." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2000. http://hub.hku.hk/bib/B31240392.
Full textFang, Weizhen. "Asymmetric Hydroalkylation of Unactivated Olefins." Thesis, Paris 11, 2014. http://www.theses.fr/2014PA112269.
Full textHomogeneous gold catalysis has been underestimated for nearly a century. After reconsideration the by chemists’ community, it rapidly became a hot topic in chemistry. To date, more than a 100 worldwide groups have embraced the golden opportunity. Considerable breakthroughs have been made, nevertheless, the classical experimental procedures still suffer from low turnover numbers (TON) and scalability. These issues can be attributed to the decay of cationic gold catalysts and several solutions have been proposed in the literature. In this thesis, we will present our way to circumvent this thorny issue. Specifically, we have used Lewis acids other than silver salts for that purpose and found that some of them could indeed generate an active gold species through slow anion metathesis. The slow anion metathesis could retard the decomposition of the active gold species. Thus, gold could be used in low amounts in scalable reactions by simply avoiding the use of silver. These silver-free two-component mixtures could address the difficult issue of C-C bond forming reaction. Besides, we have developed catalytic enantioselective hydroalkylations of unactivated alkenes. This study led us to consider indium and bismuth catalysis in addition to gold
Mangion, Bernardino. "Extending and diverting the photochemical nucleophile-olefin combination, aromatic substitution (photo-NOCAS) reaction." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 2001. http://www.collectionscanada.ca/obj/s4/f2/dsk3/ftp04/NQ66652.pdf.
Full textJiao, Guansheng. "Ketone catalyzed diastereoselective and enantioselective epoxidation of olefins : catalyst design and synthetic application /." Hong Kong : University of Hong Kong, 2000. http://sunzi.lib.hku.hk/hkuto/record.jsp?B21981772.
Full textLiu, Qingdong. "A study of the catalytic reaction of olefins with methane." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1998. http://www.collectionscanada.ca/obj/s4/f2/dsk2/tape17/PQDD_0029/NQ27188.pdf.
Full textJean, Luckner Guin J. A. "Effect of process parameters on methanol to olefins reactions over SAPO catalysts." Auburn, Ala., 2005. http://hdl.handle.net/10415/1277.
Full textTanji, Jamal. "Reaction de carboxylation d'olefines et d'alcynes par voie electrochimique : synthese de derives d'acides carboxyliques." Toulouse 3, 1987. http://www.theses.fr/1987TOU30041.
Full textBroomfield, Lewis Marc. "Synthesis of New Metal Catalysts for Reactions with a-Olefins and Cyclic Esters." Thesis, University of East Anglia, 2009. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.518370.
Full textAllgäuer, 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.
Full textPadolik, Laura Lohman. "The reactions of pentacarbonylmanganate(1-) and pentacarbonylrhenate(1-) with activated olefins and acetylenes /." The Ohio State University, 1990. http://rave.ohiolink.edu/etdc/view?acc_num=osu1487686243819214.
Full textDavis, Gwen Marie. "Interfacial Reaction of an Olefin-Terminated Self-Assembled Monolayer Exposed to Nitrogen Dioxide: An Investigation Into the Reaction Rate and Mechanism." Thesis, Virginia Tech, 2003. http://hdl.handle.net/10919/34927.
Full textMaster of Science
Gironès, i. Molera Jordi. "Aplicacions i mecanisme de la reacció d'hidroesterificació d'olefines. Compatibilització fibramatriu en poliolefines reforçades amb fibra de pi." Doctoral thesis, Universitat de Girona, 2006. http://hdl.handle.net/10803/7795.
Full textEn una segona part del treball s'han analitzat diversos sistemes de modificació superficial de fibres naturals i el seu efecte sobre la compatibilitat fibra - matriu en materials compòsits de matriu poliolefínica. S'han caracteritzat les propietats superficials de fibres de pi químicament modificades. Les fibres naturals modificades s'han utilitzat en la preparació de materials compòsits, les propietats mecàniques, tèrmiques i termomecàniques dels quals han estat caracteritzades i analitzades.
The first part of the present work exposes the results obtained during the study of the reactions of hydro and deuterioesterification of acenaphthylene. The different parameters involved in the catalitic system based on palladium complexes with phosphines have been analyzed, allowing the determination of the reaction´s mechanism. This determination has allowed the development of an enantioselective version of this reaction.
The second part deals with the chemical modification of natural fibres and their effect on the interface of natural fibre reinforced composites. The surface properties of chemically modified pine fibres have been analyzed throught several techniques. The interface compatibilization provided by such treatments has been analyzed thorough the study of the mechanical, thermal and thermomechanical properties of PP reinforced composites.
Li, Zhibin. "New micro and mesoporous materials for the reaction of methanol to olefins." Doctoral thesis, Universitat Politècnica de València, 2014. http://hdl.handle.net/10251/44229.
Full textLi, Z. (2014). New micro and mesoporous materials for the reaction of methanol to olefins [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/44229
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