This Diploma Thesis presents results obtained by solution of two partial projects: a) Preparation of monomers from renewable sources using metathesis and tandem hydrogenation catalyzed with ruthenium compounds - project solved during my Erasmus stay at the Université de Rennes 1 in France; b) Preparation and properties of ,-bis(tpy)quarterthiophene oligomers carrying ionic side groups as oligomonomers for polyelectrolyte conjugated dynamers - project solved at the Department of Physical and Macromolecular Chemistry, Faculty of Science, Charles University in Prague. Project a): Self-metathesis of 1,2-epoxyhex-5-ene (but-3-enyloxirane) and its cross-metathesis with methyl acrylate and acrylonitrile catalyzed with ruthenium compounds as well as tandem design of these metatheses and consecutive hydrogenation of their products by gaseous hydrogen have been optimized. The following influences have been studied and tuned: (i) type of the catalyst (Grubbs, Hoveyda, Zhan) and its concentration and method of dosing, (ii) concentration of reactants and additives, (iii) type of solvent, and (iv) reaction temperature. Reactions were monitored by the GC, GC and MS methods and the products were characterized by the NMR method. Methyl 6,7-epoxyheptanoate (methyl 5-oxiranylpentanoate) obtained by the tandem...

Mechanisms of three reactions catalyzed by microporous materials were investigated computationally; the reactions investigated include Friedländer and Knoevenagel reactions catalyzed by Cu3BTC2 metal organic framework (MOF) and an intramolecular cyclisation of unsaturated alcohols catalyzed by zeolite H-ZSM-5. It was found that the reaction mechanisms of all three reactions are controlled by a high concentration of active sites in materials. Reaction intermediates interact with more than one active site simultaneously. This novel concept of "multiple-site" interactions is described. The concerted effect of two catalytic sites leads to a decrease of activation barriers on reaction paths of Friedländer and Knoevenagel reactions. On the contrary, a simultaneous interaction of reactants with two active sites has a negative effect on reaction rate in case of alcohol cyclization catalyzed by H-ZSM-5; it was found that the interaction with dual sites results in the increase of activation barriers and diffusion limitations. In case of Knoevenagel reaction catalyzed by CuBTC, the adsorption of reaction precursor to the reaction site allows the creation of a dynamic defect in the MOF framework that subsequently catalyses the reaction. Both, the multiple sites effect and the dynamical defect formation effect...

5 Abstract The formerly reported hydroxyamide Ph2PfcC(O)NHCH2CH2OH 1 and its respective novel congeneric analogues Ph2PfcC(O)NHCH3−n(CH2OH)n (3: n = 2; 4: n = 3) were used to prepare a series of arene-ruthenium(II) complexes [(η6 -arene)RuCl2(L-κP)] 6-8 (arene = C6H6, p-cymene, C6Me6; L = 1, 3 or 4). These complexes were studied as pre-catalysts in redox isomerization of allylic alcohols to carbonyl compounds. Among the compounds prepared, complex 6b [(η6 -p-cymene)RuCl2(1-κP)] showed best results. The solid state structure of the product of photolytic decomposition of complex [(η6 - C6Me6)RuCl2(2-κP)] (2 = Ph2PfcC(O)N(CH2CH2OH)2), viz, [(µ-Cl)3{Ru(η6 -C6Me6)}2] [FeCl4] 9, was determined by single-crystal X-ray diffraction analysis. The bis-phosphane complexes [MII Cl2(1-κP)2] (M = trans-Pd (10), cis-Pt (11) and trans- Pt (12)) together with chalcogenide derivatives Ph2P(O)fcC(O)NH(CH2)2OH (13) and Ph2P(S)fcC(O)NH(CH2)2OH (14) derived from hydroxyamide 1 were tested in vitro for their cytotoxicity against human ovarian A2780 cancer cell line. Complexes tested showed moderate cytotoxicity. Triol-amide FcC(O)NHC(CH2OH)3 15 (Fc = ferrocenyl) reacted with decavanadate (Bu4N)2[H3V10O28] at elevated temperature and prolonged reaction time yielding the hybrid hexavanadate (Bu4N)2[{FcC(O)NHC(CH2O)3}2V6O13] 16...

This diploma thesis is focused on the design and synthesis of new half-sandwich titanium complexes for anchoring to selected supports (SiO2, SBA-15) and the study of their catalytic activity and selectivity in ethylene trimerization to 1-hexene. The synthetic strategy of half-sandwich titanium complexes with a suitable leaving group for direct anchoring through Ti−O bond was carried out (Cl, Oi-Pr). In addition, the titanium complexes with pendant alkenyl group were prepared and utilised for anchoring to a SiMe2H modified support by Pt-catalysed hydrosilylation reaction. Prepared compounds were characterised by standard spectroscopic methods (IR, NMR, MS). The heterogeneous systems were characterised by MAS NMR and IR spectroscopy, powder XRD, ICP-OES, TGA and the textural parameters were determined from nitrogen adsorption/desorption isotherms. For all prepared materials was studied the catalytic activity for ethylene trimerization and the selectivity to 1-hexene.

Plusieurs complexes de salphen à base de métaux transition (Cr, Co, Fe) ont été synthétisés et utilisés comme catalyseurs pour la copolymérisation d’époxydes avec du monoxyde de carbone (CO), des anhydrides ou du dioxyde de carbone (CO2). De nouveaux complexes à base de Zn, Al, Mg ont également été testés pour la copolymérisation d’époxydes avec CO2.La partie première s’intéresse principalement à la copolymérisation d’oxyde de propylène avec du monoxyde de carbone. Le complexe salphen de chrome et Co2(CO)8 ont été utilisées comme catalyseurs. Quel que soit le complexe utilisé, il a été observé une faible activité et les produits de carbonylation attendus (polyester et lactone) ont été obtenus en faible quantité. En revanche, la combinaison in-situ de ces deux catalyseurs a montré une activité supérieure. Cela a conduit à la formation de la lactone cyclique (β-butyrolactone) et de poly(ester-co-éther) de faible masse molaire, ce qui marque une faible compatibilité de ces complexes.La partie suivante traite de la copolymérisation d’époxydes avec des anhydrides catalysée par des complexes de salphen à base de chrome et fer ou d’une base organique simple. Les complexes utilisés sans co-catalyseur ont été inactifs, mais la combinaison avec la base organique (PPNCl) comme co-catalyseur a conduit à la copolymérisation alternée des deux monomères, produisant des polyesters avec des masses molaires jusqu’ à 10 kg.mol-1 et une faible dispersité. PPNCl s’est révélée être la base la plus efficace pour la copolymérisation alternée des époxydes et des anhydrides. Les bases organiques simples utilisées seules ont aussi permis l’obtention de polyesters, mais avec des temps de polymérisation cinq fois plus longs.Enfin, la troisième partie présente la copolymérisation des époxydes avec CO2 en présence de complexes salphen de Cr ou de Co. Les complexes salphen cobalt ont été significativement plus efficaces pour la copolymérisation de l’oxyde de propylène (PO) ou de l’oxyde de cyclohexène (CHO) avec CO2 que leurs homologues à base de chrome. Les polycarbonates obtenus avec les complexes de cobalt ont plus de 99% d’unités carbonate, des masses molaires allant de 10 à 35 kg.mol-1 et une faible dispersité. Les études cinétiques ont permis de montrer que la polymérisation est contrôlée. Des analyses par spectrométrie de masse MALDI-TOF ont permis de vérifier la microstructure et le mécanisme d’activation. Toutefois, pour la copolymérisation de PO avec CO2, les complexes salphen cobalt ont une activité plus faible (100-450 h-1) ainsi qu’une sélectivité en polycarbonate moindre (40-90%) que les complexes salen cobalt. Une sélectivité de 100% vers la synthèse de polycarbonate a néanmoins pu être obtenue lors de la copolymérisation de CHO avec CO2. Enfin, les complexes β-diminate, ketiminate et aminidate d’Al, Zn et Mg utilisés pour la copolymérisation d’époxydes avec CO2 se sont révélés décevants car présentant une activité très faible et seuls des homopolyéthers ont été obtenus. / A series of salphen complexes based on Cr, Co and Fe was synthesized and used as catalysts in ring-opening copolymerization of different substrates: (i) epoxides with carbon monoxide (CO), (ii) epoxides with anhydrides and (iii) epoxides with carbon dioxide (CO2). Additionally, a screening of catalytic activity for the last substrate was performed with novel Zn, Al and Mg non-salen based complexes.The first part of the Thesis deals with the copolymerization of propylene oxide with carbon monoxide using asymmetric salphen chromium complex and Co2(CO)8 in order to prepare a synthetic equivalent of polyhydroxybutyrate (PHB) otherwise accessible by fermentation of various substrates. Very poor catalytic performances towards carbonylated products (PHB or β-butyrolactone (BBL)) were observed with any of the two complexes. The combination of both salphen chromium and Co2(CO)8 complexes led to increased formation of BBL. Low molar mass poly(ester-co-ether) was only prepared, suggesting a poor compatibility of selected complexes.The second part of the work is focused on the copolymerization of epoxides with anhydrides catalyzed by salphen chromium or iron complexes combined with simple organic bases as cocatalysts. Salphen complexes alone were almost inactive, while in the presence of bis(triphenylphosphineiminium)chloride (PPNCl) they afforded highly alternating polyesters with molar mass up to 10 kg.mol-1 and low dispersity. Surprisingly, organic bases alone afforded similar, highly alternating polyesters at five-time lower polymerization rate. PPNCl was found to be an effective catalyst for the highly alternating copolymerization of various epoxides and anhydrides.The last part of our investigations refers to the copolymerization of epoxides with CO2 using salphen chromium and especially salphen cobalt complexes. Cobalt catalysts were significantly more active in propylene oxide (PO)/CO2 and cyclohexene oxide (CHO)/CO2 copolymerization compared to their chromium analogues. Highly alternating polycarbonates (> 99%) with low dispersity and molar mass 10-35 kg.mol-1 were prepared by salphen cobalt complexes. Kinetic studies showed that these polymerizations are controlled and MALDI-TOF MS analysis was used for initiation mechanism clarification. Compared to widely investigated salen Co catalysts, salphen Co complexes exhibit lower activity (100-450 h-1) and selectivity to polymer (40-90%) in propylene oxide/CO2 copolymerization, while 100% selectivity to polycarbonate was achieved in the copolymerization of CHO and CO2. Alternatively, new Al, Zn and Mg-based catalysts were tested for CO2 activation, however, they usually led only to epoxide homopolymerization. / V této práci byla připravena řada salfenových komplexů na bázi chromu, kobaltu a železa. Tyto komplexy byly použity jako katalyzátory pro kopolymerizace epoxidů s různými substráty: (i) s oxidem uhelnatým (CO), (ii) s anhydridy a (iii) s oxidem uhličitým (CO2). U nových komplexů na bázi zinku, hliníku a hořčíku byla dále testována možnost jejich použití jako katalyzátorů pro kopolymerizace epoxidů s CO2.První část práce se zabývá kopolymerizací epoxidů s oxidem uhelnatým s využitím asymetrického salfenového komplexu na bázi chromu a Co2(CO)8 s cílem připravit kopolymer na bázi přírodního polyhydroxybutyrátu (PHB). Salfenový komplex chromu i Co2(CO)8 vykazovaly velmi nízké aktivity při karbonylaci propylenoxidu a poskytovaly pouze nepatrné množství produktů (cyklického β-butyrolaktonu a PHB). Kombinace obou katalytických komplexů vedla k výraznému zvýšení aktivity ve prospěch cyklického produktu (β-butyrolaktonu) i polymeru. Kopolymerizací PO s CO byl získán pouze nízkomolekulární poly(ester-co-ether), což naznačuje špatnou vzájemnou kompatibilitu těchto komplexů.Druhá část je zaměřena na kopolymerizace epoxidů s anhydridy katalyzované salfenovými komplexy chromu a železa v kombinaci s jednoduchými organickými bázemi. Samotné salfenové komplexy chromu a železa nevedly ke vzniku polymeru. V kombinaci s nukleofilním kokatalyzátorem bis(trifenylfosfin)iminium chloridem (PPNCl) ovšem tyto komplexy poskytly alternující kopolymery epoxidu a anhydridu (polyestery) s molárními hmotnostmi do 10 kg.mol-1 a nízkou dispersitou. Dále bylo zjištěno, že samotné organické báze poskytují podobně jako salfenové komplexy vysoce alternující kopolymery se srovnatelnou molární hmotností i úzkou dispersitou, i když je zapotřebí 5x delších polymerizačních časů. Nejvyšší účinnost ze všech testovaných bází měl PPNCl. Tato báze byla dále efektivně použita pro kopolymerizace řady epoxidů a anhydridů za vzniku vysoce alternujících kopolymerů. Třetí část pojednává o kopolymerizacích epoxidů s CO2 s využitím salfenových komplexů chromu a kobaltu. Bylo zjištěno, že kobaltové komplexy jsou oproti chromovým mnohem efektivnější katalyzátory jak při kopolymerizacích propylenoxidu (PO) s CO2 tak i cyklohexenoxidu (CHO) s CO2. Salfenové komplexy kobaltu poskytly polykarbonáty s vysokým obsahem karbonátových jednotek v kopolymeru (> 99%), úzkou dispersitou a s molárními hmotnostmi 10-35 kg.mol-1. Studie kinetiky odhalila kontrolovaný průběh kopolymerizace. Dále byla provedena MALDI-TOF analýza výsledných polykarbonátů s cílem objasnit mechanismus iniciace kopolymerizace. Ve srovnání se salenovými komplexy kobaltu vykazují salfenové komplexy při kopolymerizacích PO s CO2 nižší aktivitu (100-450 h-1) i selektivitu na polykarbonát (40-90%). Při kopolymerizacích CHO s CO2 byla ovšem selektivita 100%. Nové komplexy na bázi Al, Mg a Zn byly také testovány jako katalyzátory pro kopolymerizace epoxidů s CO2, nicméně jejich aktivita byla nízká a výsledkem těchto reakcí byly pouze polykarbonáty s nízkým podílem karbonátových jednotek nebo polyethery.

The aim of my PhD Thesis was to explore the potential of helically chiral N-heterocyclic carbene (NHC) ligands in asymmetric catalysis. Helicenes and helicene-like molecules are inherently chiral. Their application in this field has been rather limited. To date, only a few examples of enantiopure helically chiral NHCs have been described in the literature. Using a well-established method based on the diastereoselective metal catalysed [2+2+2] cycloisomerisation of centrally chiral triynes as the key step, I have synthesised a series of optically pure 2H-pyran based penta- and hexahelicenes bearing an amino group on the terminal benzene ring. The triynes were prepared by a sequence of Sonogashira and Mitsunobu coupling reactions using the commercially available (S)-but-3-yn-2-ol as the source of chirality. The resulting aminooxa[5]- and aminooxa[6]helicenes were then converted into the corresponding 1,3-disubstituted imidazolium salts, from which, upon deprotonation, the helically chiral N- heterocyclic carbenes were generated. To evaluate the performance of the new helically chiral ligands, the enantioselective Ni0 - catalysed [2+2+2] intramolecular cycloisomerisation of prochiral triynes to nonracemic dibenzohelicenes was chosen as a model reaction. All the synthesised imidazolium salts provided,...

Hydrogen processing is becoming increasingly important not only in the production of electricity but also during its accumulation. One of the energy storage options are liquid organic hydrogen carriers (LOHC). The main drawback of LOHC is the need for a large amount of thermal energy to release molecular hydrogen. We can bypass this issue using heterogeneous catalysis by transferring hydrogen from LOHC to acetone and using the produced 2-propanol (IPA) in the fuel cell. This innovative strategy of getting electri- cal energy from LOHC can be potentially energetically neutral. In this work, we studied highly ordered Co3O4(111) model catalysts for IPA oxidation in the as-prepared state and enhanced with platinum (Pt) nanoparticles. Catalysts were prepared by Physical Vapour Deposition (PVD) and further investigated by means of Low Energy Electron Diffrac- tion (LEED), X-ray Photoelectron Spectroscopy (XPS), Scanning Tunneling Microscopy (STM) and Temperature Programmed Desorption (TPD). The nucleation process of Pt on the as-prepared Co3O4(111) surface was studied by depositing low amounts 0.04 and 0.13 monolayer (ML) of Pt, that create clusters as small as 2 or 3 atoms with no need for a special nucleation site. We have identified the formation of Pt-induced defects in the atomically flat cobalt oxide...

We investigate a nonlinear reaction-diffusion system coupled with convection- diffusion system. This combined system corresponds to physical description of heteroge- neous catalysis when the flow of bulk-constituents is driven by a given stationary velocity field; diverse mechanisms between bulk- and surface-parts of the model-domain are de- scribed by Langmuir-Hinshelwood absorption kinetics; and the irreversible reactions on the catalytic walls meets the law of mass action with quadratic rate. The first part of the thesis is focused on analytical results; in Chapter 2 we prove existence and unique- ness of a mild solution for so-called near-by problem using nonlinear semigroup theory; in Chapter 3 we investigate the weak formulation of the problem. We prove an existence of a weak solution for little modified problem which, under an assumption, coincides with the original problem. In the second part of the thesis (Chapter 4) we numerically investigate the evolution of the bio-diesel microreactor. We compute numerical solutions using several methods and we test the results by analytical and physical conditions; with the aim to find the most efficient way to compute precise and physically correct solution. Keywords: heterogeneous catalysis, coupled reaction-diffusion/convection-diffusion system, nonlinear...

This thesis consists of two parts discussing modelling of heterogeneous catalytic reactors. In the first one, an industrial prototype of a fluidized bed reactor serving as a hydrogen generator based on endothermic decomposition of formic acid is studied. After initial determination of the main reactor characteristics a system of nine con- stituents is derived and, consequently, reduced to a three phase flow. The solid and bubble particles immersed in a liquid are modelled by the Basset-Boussinesq- Ossen equation. Furthermore, an averaging technique is used to derive a three phase Euler-Euler model. Finally, numerical computations with a verification towards the measurements and a CFD analysis are proceeded. The second part discusses interfacial transport phenomena between a bulk and catalytic surfaces of a reactor mediated via the boundary conditions. The constitu- tive relations, that by construction comply with the second law of thermodynamics, follow from the specification of suitable thermodynamic potentials together with an identification of the bulk and surface entropy productions. The derived model is suitable for further analysis providing clear guidelines for the incorporation of the Langmuir-type adsorption model as well as other sorption models. Keywords: Heterogeneous catalysis, multi-phase...

Electron confinement due to the two-dimensional (2D) nature of layered materials accounts for their fascinating electronic properties and for their applications in new-generation electronic devices. Moreover, the large specific surface area of 2D materials also enables their use in surface-related applications, such as catalysis and adsorption. In addition, these 2D materials are promising photocatalysts thanks to the shorter migration distance of photogenerated electrons and of electron holes. The research reported in this thesis aimed to provide atomistic insight into 2D layered materials, particularly into their structures, electronic properties and potential applications in the field of catalysis, photocatalysis and alkali metal ion batteries. Our findings are not only theoretically relevant but also open new research avenues for our experimental collaborators to improve specific properties and activities of their materials. The main results from this thesis, for five different classes of 2D materials, are summarized below. 2D covalent organic frameworks (COFs). CTF-type COFs with similar topology but different nitrogen-to-carbon ratios were investigated for their potential in photocatalytic water splitting. More specifically, torsion and bending effects on structure stability were investigated in...