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Ferrocene stibane ligands
Antala, Jakub ; Štěpnička, Petr (advisor) ; Gyepes, Róbert (referee)
5 Title: Ferrocene stibane ligands Author: Jakub Antala Department: Department of Inorganic Chemistry Supervisor: prof. RNDr. Petr Štěpnička, Ph.D., DSc. Abstract: This diploma thesis reports a study into the coordination properties of ferrocene phosphino-stibine Cy2PfcSbPh2 (LCy, Cy = cyclohexyl, fc = ferrocene-1,1'-diyl). Complexes with various transition metals were prepared (RuII , RhIII , PtII , PdII , AuI ), where the ligand binds in monodentate, bridging or chelating mode. Ruthenium(II) and rhodium(III) complexes were prepared from precursors with π-coordinated arene ligands, whereas [MCl2(η2 :η2 cod)] (M = Pd, Pt; cod = 1,5-cyclooctadiene) precursors were used to prepare palladium(II) and platinum(II) complexes and synthesis of gold(I) complexes started from [AuCl(tht)] (tht = tetrahydro- thiophene). In addition, the thesis describes the reactivity of ferrocene phosphino-stibine Ph2PfcSbPh2 (LPh). Specifically, it focuses on the preparation of chalcogenides Ph2P(E)fcSbPh2 (E = O, S, Se) and the corresponding stiborane derivatives Ph2P(E)fcSbPh2(O2C6Cl4) (E = void, O, S, Se), in which the stiborane center bears tetrachloropyrocatechol substituent, which makes it Lewis acidic and potentially prone to behave as an acceptor of electron pair from the Ph2P(E) moiety. The presence of this interaction was...
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Synthesis of gold(I) carbene complexes from isocyanoferrocene
Harmach, Petr ; Štěpnička, Petr (advisor) ; Gyepes, Róbert (referee)
Title: Synthesis of gold(I) carbene complexes from isocyanoferrocene Author: Petr Harmach Department: Katedra anorganické chemie Supervisor: prof. RNDr. Petr Štěpnička, Ph.D., DSc. Abstract: The objective of this bachelor thesis was the synthesis of gold(I) carbene complexes. These complexes were synthetised from a newly prepared gold(I)-isocyanoferrocene complex and also directly from isocyanoferrocene. Carbene complexes were obtained from primary and secondary amines, and therefore complexes contain disubstituted or trisubstituted diaminocarbene moieties. All newly prepared complexes were characterized by NMR spectroscopy, mass spectrometry, elemental analysis and infrared spectroscopy. The structures of the majority of the prepared complexes were confirmed by single-crystal X-ray diffraction analysis. Key words: isocyanides, ferrocene, carbenes, gold(I) complexes
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Preparation of P,N-donor ferrocene ligands by coupling reactions
Rezazgui, David ; Schulz, Jiří (advisor) ; Gyepes, Róbert (referee)
Title: Preparation of P,N-donor ferrocene ligands by coupling reactions Author: Bc. David Rezazgui Department: Department of Inorganic Chemistry Supervisor: RNDr. Jiří Schulz, Ph.D. Abstract: P,N-donor ligands form a varied group of compounds with wide utilization in homogeneous gold catalysis. This group of ligands uses geometrical features of moieties to which the donors are attached and the difference in hardness of the donor groups resulting in their unique coordination behavior. Ferrocene moiety offers unique geometrical features and flexibility. The chemical stability of ferrocene makes it possible to use various synthetic methods like cross- coupling reactions which are commonly used in organic synthesis. This work describes the preparation of six P,N-donor ferrocene ligands via Negishi cross-coupling reaction and their gold complexes which were further tested in catalytic cyclization of N-(prop-2-yn-1- yl)benzamide and oxidative cyclization of phenylacetylene. The electron richness of the phosphine donor moieties was assessed by measuring of 1 JSeP interaction constant of the corresponding selenides. In this work a general synthetic route to hetero- and homoannularly substituted P,N-donor ferrocene ligands of catalytically active complexes was introduced. Keywords: ferrocen, hybrid ligand, gold...
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Preparation and characterization of new materials for metathesis and adsorption
Pastva, Jakub ; Čejka, Jiří (advisor) ; Gyepes, Róbert (referee) ; Koubek, Josef (referee)
The main objective of this work was to evidence versatile applications of ordered siliceous mesoporous materials, especially in adsorption and catalysis. For these reasons four mesoporous molecular sieves (SBA-15, SBA-16, MCM-41, and MCM-48) with different structures and textural properties have been chosen. To show the possible application of mesoporous molecular sieves as a CO2 adsorbent, magnesium oxide, and potassium carbonate were incorporated into SBA-15, SBA-16, and MCM-48 silicas. In order to avoid destruction of silica supports, a novel procedure based on the precipitation of magnesium acetate on the silica surface was developed. Subsequent in situ chemical conversion of magnesium acetate provided magnesium oxalate, while magnesium oxide was formed by calcination. To introduce potassium carbonate, silica modified with MgO was impregnated with potassium oxalate followed by its conversion to carbonate. All prepared mesoporous adsorbents preserved characteristic features of mesoporous molecular sieve (large surface areas, narrow pore size distributions). The comparison of carbon dioxide isotherms obtained on prepared samples revealed that their adsorption properties are influenced by the type of mesoporous structure. The SBA-15 silica containing magnesium oxide and promoted by potassium...
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Aminophosphinic acids
Kruliš, Tomáš ; Kubíček, Vojtěch (advisor) ; Gyepes, Róbert (referee)
Two phosphinic acids were prepared: 1-hydroxy-ethan-1,1-bis[N,N- bis(karboxymethyl)aminomethyl]phosphinic acid; H6L1 and methylenebis[N,N- bis(karboxymethyl)aminomethyl]phosphinic acid; H6L2 . Acid-base and complexation properties were studied by potenciometric titrations. Complexes of both ligands with Cu2+ ions were studied in detail using UV/VIS spectrometry. Keywords: Organophosphorus synthesis, bisphosphinic acids, coordination properties
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Reactivity of a ferrocene distibane
Antala, Jakub ; Štěpnička, Petr (advisor) ; Gyepes, Róbert (referee)
5 Title: Reactivity of ferrocene distibane Author: Jakub Antala Department: Department of Inorganic Chemistry Supervisor: prof. RNDr. Petr Štěpnička, Ph.D., DSc. Consultant: RNDr. Jiří Schulz, Ph.D. Abstract: The aim of this bachelor thesis is preparation of 1,1'-bis(diphenylstibino)ferrocene (L), an antimony analogue of the widely studied ligand 1,1'-bis(diphenylphosphino)ferrocene and study into its coordination properties. Two ruthenium(II) (1, 3) and two rhodium(III) complexes (2, 4) were prepaired, in which the ligand L coordinates as bridging or chelating ligand. Two ruthenium(II) and one rhodium(III) precursors with π-coordinated arene ligands were used for the preparation of complexes. When preparing chelate complexes, sodium hexafluorophosphate was also necessary. All complexes were characterised by NMR spectroscopy, mass spectrometry, elemental analysis and crystal structure was determined by X-ray structural analysis. The structures of the stibine complexes were compared with their analogs resulting from 1,1'-bis(diphenylphosphino)ferrocene. Key words: ferrocene, stibines, complexes, ruthenium, rhodium, structure elucidation
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