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Coordinatively unsaturated complexes with potential nucleasic activity
Willimetz, Robert ; Kotek, Jan (advisor) ; Schulz, Jiří (referee)
Biofilms are bacterial colonies attached to the surfaces through matrix of the biopolymer substances they produce. These biofilms can also form on medical implants, where they are responsible for difficult-to-treat chronic infections. One approach to prevent biofilm formation may be using of coordination compounds with nuclease activity. These compounds contain a hydrolytically active metal ion that is able to actively cleave extracellular DNA to prevent matrix and biofilm formation. The aim of this diploma thesis was to prepare a series of Cu(II) complexes of 1,4,7-triazacyclononane derivatives and to observe their potential nuclease activity. One of the complexes was a 1,4,7-triazacyclononane derivative with a thiazole anchor. Prepared complex can be incorporated through this anchor into polymers to a surface with potential ability to prevent biofilm formation.
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Application of modern analytical methods for the study of selected boron coordination compounds
Hrušková, Helena ; Jelínek, Ivan (advisor) ; Dian, Juraj (referee)
This thesis is focused on the study of boron coordination compounds, specifically boron pyrogallol and 2,3-dihydroxynaphthalene ligand complexes. In the introductory part of the work are discussed the properties of boron compounds, their preparation, the possibility of separation by capillary electrophoresis and methods of structural characterization. In the first part of the thesis, the methods of preparation of complexes are discussed and for each complex the optimal yield response is chosen. The resulting products were studied by low resolution mass spectrometry. In the second part of the thesis, structures of complexes, including their modeling in the Gaussian program, were described more precisely. Furthermore, the complexes were characterized by high resolution mass spectrometry. The complexes were also studied by 11 B, 1 H and 1 H COSY NMR and IR spectroscopy. The third part was devoted to the separation of these substances from the mixture after the reaction. CE-UV and CE-MS techniques were used for this purpose. To convert the results, the separation method was developed in ammonium formate buffers that are compatible with both instruments. The equilibration between complexes and ligands was also monitored by CE-UV. A special chapter is the study of pyrogallol autooxidation by UV-VIS and...
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Phosphinoferrocene amides and hydrazides
Solařová, Hana
Title: Phosphinoferrocene amides and hydrazides Author: Hana Solařová Department: Department of Inorganic Chemistry Supervisor: doc. RNDr. Petr Štěpnička, Ph.D. Abstract: While studying functionalized phosphinoferrocene ligands, we recently turned to phosphinoferrocene carboxamides. These donors already proved to be versatile ligands for coordination chemistry and catalysis. This led us to synthesize and study the archetypal representative, 1'-(diphenylphosphino)-1-carbamoylferrocene (5), and the corresponding hydrazide 6. PPh2 COOH Fe Hdpf PPh2 CONH2 Fe 5 PPh2 CONHNH2 Fe 6 This work describes the preparation of primary amide 5 and hydrazide 6 from 1'- (diphenylphosphino)-1-ferrocenecarboxylic acid (Hdpf) via the corresponding acylbenzo- triazole derivative. The hydrazide was alternatively obtained from Hdpf methylester and hydrazine hydrate. Both newly synthesized compounds were characterized by spectroscopic methods (NMR, IR, and MS) and elemental analysis, and their crystal structures were determined by single-crystal X-ray crystallography. The amide was further utilized in the preparation of several palladium complexes, which were characterized in a similar manner including X-ray crystallography. One palladium complex was obtained also from the hydrazide. However, the hydrazide was used mainly as a...
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Ferrocene phosphinoguanidine donors
Bárta, Ondřej ; Štěpnička, Petr (advisor) ; Dostál, Libor (referee) ; Hoskovcová, Irena (referee)
The "Ferrocene phosphinoguanidine donors" project presented in this Thesis targeted on the synthesis, coordination chemistry and catalytic applications of a rather uncommon class of compounds combining phosphine and guanidine functional groups in their molecules. Two series of such compounds based on ferrocene backbone (henceforth fc = ferrocen-1,1΄-diyl) were studied. Firstly, a reliable synthetic route towards polar phosphinoguanidinium chlorides [R2PfcCH2NHC(NH2)2]Cl, where R = iso-propyl, cyclohexyl, phenyl and 2-furyl, was developed and these ligands were tested as supporting ligands in palladium-catalysed Suzuki-Miyaura-type reactions in biphasic aqueous mixtures and in rhodium-catalysed hydroformylation of 1-hexene. Deduced from the results, the hydrophilic guanidinium tag had a beneficial effect on the catalytic activity and, particularly, the electron-rich phosphines from this series could serve as a useful alternative to commonly used ligands for catalytic applications in polar or aqueous reaction media. Phosphinonitriles R2PfcCN obtained as intermediates during the synthesis of the abovementioned ligands were additionally used for the preparation of the dimeric complexes [Au2(µ-R2PfcCN)2][SbF6]2, in which the gold(I) centre was stabilised by nitrile coordination. These complexes proved...
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Application of modern analytical methods for the study of selected boron coordination compounds
Hrušková, Helena ; Jelínek, Ivan (advisor) ; Dian, Juraj (referee)
This thesis is focused on the study of boron coordination compounds, specifically boron pyrogallol and 2,3-dihydroxynaphthalene ligand complexes. In the introductory part of the work are discussed the properties of boron compounds, their preparation, the possibility of separation by capillary electrophoresis and methods of structural characterization. In the first part of the thesis, the methods of preparation of complexes are discussed and for each complex the optimal yield response is chosen. The resulting products were studied by low resolution mass spectrometry. In the second part of the thesis, structures of complexes, including their modeling in the Gaussian program, were described more precisely. Furthermore, the complexes were characterized by high resolution mass spectrometry. The complexes were also studied by 11 B, 1 H and 1 H COSY NMR and IR spectroscopy. The third part was devoted to the separation of these substances from the mixture after the reaction. CE-UV and CE-MS techniques were used for this purpose. To convert the results, the separation method was developed in ammonium formate buffers that are compatible with both instruments. The equilibration between complexes and ligands was also monitored by CE-UV. A special chapter is the study of pyrogallol autooxidation by UV-VIS and...
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Synthesis and coordination behaviour of 3-(diphenylphosphino)propanamide
Řežábková, Jana ; Štěpnička, Petr (advisor) ; Havlíček, David (referee)
This bachelor thesis describes the synthesis of 3-(diphenylphosphino)propanamide (compound 1) and subsequent preparation of two palladium(II) complexes with the synthesized phosphinoamide ligand. The coordination behaviour of 3-(diphenyl- phosphino)propanamide is discussed. In complex [PdCl(LNC )(Ph2PCH2CH2C(O)NH2-κP)] (compound 2) the phosphinoamide 1 exhibits P-monodentate coordination, whereas in the cationic complex [Pd(LNC )(Ph2PCH2CH2C(O)NH2-κ2 O,P)]ClO4 (compound 3) it binds as a P,O-chelating bidentate ligand. (LNC = 2-[(dimethylamino-κN)methyl]phenyl-κC1 ). 1 2 3 The ligand was synthesized by base-catalysed addition of diphenylphosphine across the double bond of acrylamide. Both complexes were prepared from [PdCl(LNC )]2 as metal precursor. All substances were characterised by common analytical methods, specifically by NMR spectroscopy, mass spectrometry, infrared spectroscopy and elemental analysis. Crystals of both complexes were obtained and their crystal structure was determined using X-ray crystallography.
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Phosphinoferrocene amides and hydrazides
Solařová, Hana
Title: Phosphinoferrocene amides and hydrazides Author: Hana Solařová Department: Department of Inorganic Chemistry Supervisor: doc. RNDr. Petr Štěpnička, Ph.D. Abstract: While studying functionalized phosphinoferrocene ligands, we recently turned to phosphinoferrocene carboxamides. These donors already proved to be versatile ligands for coordination chemistry and catalysis. This led us to synthesize and study the archetypal representative, 1'-(diphenylphosphino)-1-carbamoylferrocene (5), and the corresponding hydrazide 6. PPh2 COOH Fe Hdpf PPh2 CONH2 Fe 5 PPh2 CONHNH2 Fe 6 This work describes the preparation of primary amide 5 and hydrazide 6 from 1'- (diphenylphosphino)-1-ferrocenecarboxylic acid (Hdpf) via the corresponding acylbenzo- triazole derivative. The hydrazide was alternatively obtained from Hdpf methylester and hydrazine hydrate. Both newly synthesized compounds were characterized by spectroscopic methods (NMR, IR, and MS) and elemental analysis, and their crystal structures were determined by single-crystal X-ray crystallography. The amide was further utilized in the preparation of several palladium complexes, which were characterized in a similar manner including X-ray crystallography. One palladium complex was obtained also from the hydrazide. However, the hydrazide was used mainly as a...
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Phosphinoferrocene amides and hydrazides
Solařová, Hana ; Štěpnička, Petr (advisor) ; Kubíček, Vojtěch (referee)
Title: Phosphinoferrocene amides and hydrazides Author: Hana Solařová Department: Department of Inorganic Chemistry Supervisor: doc. RNDr. Petr Štěpnička, Ph.D. Abstract: While studying functionalized phosphinoferrocene ligands, we recently turned to phosphinoferrocene carboxamides. These donors already proved to be versatile ligands for coordination chemistry and catalysis. This led us to synthesize and study the archetypal representative, 1'-(diphenylphosphino)-1-carbamoylferrocene (5), and the corresponding hydrazide 6. PPh2 COOH Fe Hdpf PPh2 CONH2 Fe 5 PPh2 CONHNH2 Fe 6 This work describes the preparation of primary amide 5 and hydrazide 6 from 1'- (diphenylphosphino)-1-ferrocenecarboxylic acid (Hdpf) via the corresponding acylbenzo- triazole derivative. The hydrazide was alternatively obtained from Hdpf methylester and hydrazine hydrate. Both newly synthesized compounds were characterized by spectroscopic methods (NMR, IR, and MS) and elemental analysis, and their crystal structures were determined by single-crystal X-ray crystallography. The amide was further utilized in the preparation of several palladium complexes, which were characterized in a similar manner including X-ray crystallography. One palladium complex was obtained also from the hydrazide. However, the hydrazide was used mainly as a...
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