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Functional phosphinoferrocene carboxamides
Schneiderová, Barbora ; Štěpnička, Petr (advisor) ; Vojtíšek, Pavel (referee)
Functionalized amides 3 and 4 were prepared by the reaction of 1'-(diphenylphosphino)ferrocene-1- carboxylic acid (Hdpf) with 2-(diphenylphosphino) ethylamine or 2-N,N'- (dimethylamino)ethylamine. The amides were converted to their respective phosphinsulfides 5 and 6. Addition of MeI to the solution of 6 gave ammonium salt 7 which, after desulfuration with Raney nickel afforded ammonium salt 8. Compounds 3-8 were characterized by NMR and IR spectroscopy and by MS spectrometry. Phosphine sulfides 6 and polar amides 7 and 8 were structurally characterized. Amides 3, 4 and 8 were tested as ligands in Pd-catalyzed Suzuki-Miyaura coupling reaction of phenylboronic acid with 4-bromacetophenone in organic solvent, water and in biphasic system. Amides 3 and 4 and the related amides 1'-(diphenylphosphanyl)-1-[N-{3- (diphenylphosphino)propyl)}carbamoyl]ferrocene(1) and 1'-(diphenylphosphanyl)-1-[N-(3- dimethylaminopropyl)carbamoyl] ferrocene (2) were reacted with [(COD)PdCl2] to afford palladium complexes of the general formula [(L)PdCl2]. These compounds were characterized by NMR and IR spectroscopy and by MS spectrometry and, for selected representatives, also by X-ray diffraction analysis. Keywords: ferrocene, phosphinoamides, palladium, coordination study, catalysis, Suzuki-Miyaura cross-coupling reaction.
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Homologous ferrocene phosphines
Vosáhlo, Petr ; Štěpnička, Petr (advisor) ; Vojtíšek, Pavel (referee)
Title: Homologous ferrocene phosphines Author: Bc. Petr Vosáhlo Department: Department of Inorganic Chemistry Supervisor: prof. RNDr. Petr Štěpnička, Ph.D., DSc. Abstract: This thesis describes the synthesis and coordination behaviour of ferrocene diphosphines derived from 1,1'-bis(diphenylphosphino)ferrocene (dppf). Dppf is one of the most succesful ferrocene ligands, which can be used in various metal-catalyzed reactions. This study aimed to prepare analogous ligands with one dialkylphosphino substituent and one (diphenylphosphino)methyl group. These ligands were oxidized by KSeCN to afford the corresponding phosphinoselenides. The phosphinoselenides were used to assess sigma-donor abilities by measuring the coupling constant 1 JSeP via 31 P NMR spectroscopy. Lastly, the coordination behaviour of these ligands in palladium complexes was studied. The homologous ligands usually formed a mixtures containing a chelate complex and dimeric species with trans- coordinated ligands. Key words: ferrocene, phosphines, homologous ligands, palladium(II) complexes, structure elucidation.
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Alternative synthesis of of 1-(diphenylphosphino)-1'-(N,N-dimethylaminomethyl)ferrocene
Zábranský, Martin ; Štěpnička, Petr (advisor) ; Vojtíšek, Pavel (referee)
An alternative, more straightforward and effective method for the preparation of 1- (diphenylphosphino)-1'-(N,N-dimethylaminomethyl)ferrocene was developed using 1-bromo- 1'-(diphenylphosphino)ferrocene as the starting material and Eschenmoser's salt as an aminomethylation agent. Purity of thus prepared phosphinoamine was verified by 1 H and 31 P NMR spectroscopy and by comparison of the data with those reported in the literature (M. E. Wright, Organometallics, 1990, 9, 853). The coordination chemistry of this compound was investigated in gold(I) complexes. Thus, chlorido[1-(diphenylphosphino)-1'-(N,N-dimethyl- aminomethyl)ferrocene]gold(I) complex was synthesized and converted to ill-defined [1- (diphenylphosphino)-1'-(N,N-dimethylaminomethyl)ferrocene]gold(I) perchlorate by halogen abstraction with AgClO4. Protonization of the nitrogen atom in both compounds with hydrogen chloride yielded the corresponding hydrochlorides. It was shown that 1- (diphenylphosphino)-1'-(N,N-dimethylaminomethyl)ferrocene is coordinated as a simple phosphine in the resulting complexes while its amine nitrogen is protonated. All these complexes were characterized by means of 1 H, 31 P and 13 C NMR spectroscopy, mass spectroscopy with electrospray ionisation, elemental analysis and by single-crystal X-ray diffraction analysis.
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Macrocyclic ligands for selective complexation of large cations
Šefčík, Martin ; Kotek, Jan (advisor) ; Vojtíšek, Pavel (referee)
4 Abstract Nowadays, macrocyclic complexes of actinides receive an increasing attention for their potential applications in radiotherapy. It requires significant demands on their thermodynamic and kinetic stability which are particularly influenced by an appropriate choice of a ligand. This Thesis focuses on a synthesis and characterization of two ligands that are potentially applicable for complexation of lanthanum as a model of radioactive actinium. Both ligands are based on a fifteen-membered cycle containing pyridine group, 15-pyN3O2. The first ligand, H4L1, contains two phosphonate pendant arms. The second ligand, H2L2, contains two phosphinate pendant arms. Both compounds were prepared and characterized. Keywords Macrocyclic ligands, large cations, phosphonic acids, phosphinic acids, dissociation constants
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Coordination chemistry of pharmaceuticals
Malová, Zuzana ; Lukeš, Ivan (advisor) ; Vojtíšek, Pavel (referee)
Present methods for diagnosis of neurodegenerative diseases are rather limited and in clinical practise are missing. This thesis is focused on utilization of the positron emission tomography using isotope 64 Cu(II). For the project, two contrast agents were proposed containing ligand for Cu (II) coordination and thioflavine T derivative as fluorescent dye, also as a targeting compound. Structure of the thioflavine T derivative was defined by X-ray structural analysis. The selected fluorescent dye has a high affinity for incipient amyloids and, when bound to their structure, has enhanced fluorescent properties. The proposed ligands are tetraazacyclic. The first one is a diamide, where the thioflavin T derivative is part of a macrocyclic ring. The second selected ligand is linked to the thioflavin T derivative via a linker. Key words: complexes; pharmaceuticals; transition metals
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Cyclam derivatives with coordinating bifunctional groups in 1,8 positions for selective copper(II) complexation
Hörnerová, Alžběta ; Kotek, Jan (advisor) ; Vojtíšek, Pavel (referee)
Copper radionuclides are the object of increasing interest due to their advantageous properties for use in tumor diagnostics (PET, SPECT) and radiotherapy. In order to accomplish the best biodistribution the metal ion needs to be complexed by a suitable ligand attached to a biologically active molecule. The aim of this thesis is the synthesis of asymmetrically disubstituted derivatives of 1,4,8,11-tetraazacyclotetradecan (cyclam) with methylphosphonate and methylphosphinate pendant arms in 1,8 positions. Although the synthesis of designed ligands failed, the obtained knowledge will be used in further approaches of preparation of these compounds. Keywords: radiotherapy, SPECT, PET
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Radiolabeling of aluminum and gallium complexes with radioisotope 18F
Kuncová, Lucie ; Kubíček, Vojtěch (advisor) ; Vojtíšek, Pavel (referee)
The most widely used emitter in positron emission tomography is the fluorine isotope 18 F, which can bind to a number of atoms, and thus allows the formation of imaging agents for positron emission tomography. This work will summarize methods for labeling complexes containing aluminum or gallium as a central cation, which can serve as stable carriers of the positron emitter in a human body. Both of these elements have unique physical and chemical properties suitable for molecular imaging. Therefore the development of complex labeling, their structure, coordination environment and some applications in nuclear medicine will be described here.
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Activation of ferrocene ligands by sandwich complexes of Group 4 metals
Kout, Matyáš ; Štěpnička, Petr (advisor) ; Vojtíšek, Pavel (referee)
This bachelor thesis deals with synthesis, reactivity and characterization of compounds resulting from the reactions of substituted ferrocene ligands with electron- deficient complexes of group 4 transition metals in oxidation state II with the aim of finding experimental conditions for preparation of complexes containing two metal atoms in one molecule. Reactions were performed under inert atmosphere and the products were crystallized. The obtained crystals were subjected to X-ray diffraction analysis and to NMR spectroscopy in order to elucidate molecular structure of the isolated products. Along the way, instability of the prepared compounds towards air oxygen and moisture has surfaced, though it also led to a discovery of several original compounds. Among these, the molecule containing peroxide ligand bonded to zirconocene fragment is worth noting as a fine example of oxygen molecule activation with low oxidative state complexes of transition metals.
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Structure analysis of molecular crystals
Janíček, Jakub ; Císařová, Ivana (advisor) ; Vojtíšek, Pavel (referee)
Summary: Diploma thesis covers characterization of molecular crystals by X-ray structural analysis. N-carbamimidazoylisonikotinamid and 1-phenylguanidin were chosen, because their potential use in second harmony generation. Their salts with inorganic acids were prepared and determined their structures. Phase transition of 4,6-diaminopyrimidinium nitrate was studied by x-ray diffraction and differential scanning calorimetry. This phase transition is accompanied by thermosalient effect, causing that the crystals jump. Keywords: thermosalient, jumping crystal, X-ray diffraction, non-linear optics, N-carbamimidazoylnikotinamid, 1-phenylguanidin, 4,6diaminopyrmidin.
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Applied Mineralogy in Forensic Science field
Kotrlý, Marek ; Matějka, Dobroslav (advisor) ; Kopecká, Ivana (referee) ; Vojtíšek, Pavel (referee)
1 ABSTRACT Surprisingly, applied mineralogy plays an important role in the forensic science field. It is the miner- alogical phases which exist in many kinds of materials and traces but also the mineralogical analysis procedures which are often used in the field of so called trace evidence. For purposes of this study, 4 important fields of forensic microanalysis were chosen. These are those fields in which applied min- eralogy is applied and which characterize the width and heterogeneity of the concerned area. Powder X-ray microdiffraction plays quite an important and irreplaceable role not only in the direct phase analysis of substances in mixtures. The author designed, tested and introduced a set for centra- tion and direct check of the analysed surface during micro-diffraction analysis and also experimentally optimised sensing parameters for the different system configuration. A possibility to calculate the size of the nanoparticles (more precisely the size of a mono crystal domain) was tested. XRD methods ap- plication allows refining organic analysis for example in the case of new synthetic drugs. Micro diffrac- tion was also used for the first complex phase analysis of colour layers of the altar in the chapel in the castle of Křivoklát (dated 1480 - 1490). Forensic analysis of soil phases used to be,...
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