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Synthesis of gold(I) biscarbene complexes with ferrocenyl substituents
Franc, Michal ; Štěpnička, Petr (advisor) ; Růžička, Aleš (referee)
Title: Synthesis of gold(I) biscarbene complexes with ferrocenyl substituents Author: Bc. Michal Franc Institution: Faculty of Science, Charles University in Prague, Department of Inorganic Chemistry Supervisor: prof. RNDr. Petr Štěpnička, Ph.D., DSc. Abstract: Coordination-activated isocyanides attracted attention after it was found that carbene complexes could be readily prepared from them by addition reactions of protic nucleophiles. Carbenes have attracted much interest in recent years as a new class of ligands for transition metals and catalysis. Their advantage is their ability to stabilize catalytically active centers and thereby accelerate catalytic processes. This work presents the preparation of biscarbene gold(I) complexes with ferrocene substituents via addition reactions of amines. The starting material was a bis(isocyanoferrocene)gold chloride, which was the reaction of amines to Fischer-type protic carbenes by reactions with amines. Further, bis(isocyanoferrocene)gold(I) perchlorate was prepared and from it bis(isocyanoferrocene)gold(I) complex was synthesised by addition reaction of mofoline. All newly prepared compounds (Scheme 1), except compound 1, were characterized by NMR (except insoluble compound 5), IR spectroscopy, elemental analysis, MS and their solid state structure was...
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Study of various materials for solar cells-
Růžička, Aleš ; Toušková, Jana (advisor) ; Prokeš, Jan (referee)
Sluneční články jsou slibnou a rozvíjející se alternativou ke klasickým zdroj·m elektrické energie. V této práci studujeme r·zné parametry křemíkových a organických slunečních článk·. Ze získa- ných temných voltampérových charakteristik křemíkového článku naměřených při více teplotách byl určen mechanismus transportu náboje v porovnání s teoretickými modely. Taktéž u organické vrstvy polymeru P3CT byl z temné voltampérové charakteristiky za pokojové teploty navržen me- chanismus transportu náboje. Pro měření voltampérových charakteristik slunečních článk· za osvětlení byl použit simulátor slunečního záření. Z naměřených osvětlených voltampérových charakteristik byly určeny výstupní parametry křemíkových a organických slunečních článk·, přičemž byl kladen d·raz na účinnost přeměny sluneční energie na energii elektrickou. Zjištěná účinnost křemíkového článku byla η = 13, 21% a maximální účinnost organických článk· byla η = 1, 51%.
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Synthesis and Use of Transition Metal Complexes with Helical Ligands
Žádný, Jaroslav ; Vojtíšek, Pavel (advisor) ; Kotora, Martin (referee) ; Růžička, Aleš (referee)
The Thesis describes our successful endeavour to develop asymmetric synthesis of functionalized 2H-pyran or 2,7-dihydrooxepine helicene-like compounds in an optically pure form. These helicene surrogates were fully characterized and their use in enantioselective catalysis as chiral ligands, organocatalysts or chiral modifiers was explored. A general method for the preparation of optically pure [5]- and [6]heterohelicenes by asymmetric synthesis is based on highly diastereoselective [2+2+2] cycloisomerization of centrally chiral triynes mediated/catalyzed by transition metal complexes. Stereochemical outcome of the cyclization process is controlled by 1,3-allylic-type strain. This new methodology is highly versatile providing an easy access to chiral ligands, organocatalysts or modifiers in a nonracemic form. Optically pure 2,7-dihydrooxepine [5]helicene-like phosphite ligands were explored in enantioselective allylic amination under catalysis by iridium(I) complexes to reach up to 82% ee. An organocatalysts represented by the optically pure 2H-pyran [5]helicene-like DMAP analogue was synthesized and applied to kinetic resolution of racemic sulfoximines. Finally, various functionalized derivatives of helicenes and helicene-like compounds (azahelicenes, DMAP analogues, (thio)urea derivatives) were...
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Polycyclic tetraazamacrocycles
Plutnar, Jan ; Hermann, Petr (advisor) ; Podlaha, Jaroslav (referee) ; Růžička, Aleš (referee)
Two series of new bicyclic tetraazamacrorycles built up on skeletons of either 1,5,8,12-tetraazabiryclo[10.2.2]hexadecane (1,4-en-cyclam) I or 1,4,8,11- tetraazabicyclo[6.6.2]hexadecane (1,8-en-ryclam) 8 were prepared. The 1,4- en.cyc|am-based unsymmetrica| compounds bearing the pnitrobenzy| moieý (precursor for a biomolecule-conjugation) were synthesised exploiting the low so|ubi|iý of the intermediate quaternary derivative 2 in non-po|ar so|vents. The |igands 3 and 6 exhibited the expeďed comp|exing abi|ity towards copper(Il) and zinc(Il) although the complexation proceeded relatively slowly (at room temperature in order of hours). The mďa| comp|exes thus formed exhibited thermodynamic stability constants lower than those repofted for similar monoryclic tetraazamacrocycles (cyclam, Me+cyclam) probably due to inadvisability of the conformational change (chair or twisted-boat -> boat conformation of the piperazine subunit) conneďed to the metaI ion encapsulation. On the other hand, when the stability of coppe(Il) complex of 3 is compared to stabi|iý constant reported for the biryc|ic amine 1, the trend in the values of these constants is the same for the couple ligand I - ligand 3 as for the couple cyclam - Me+cyclam. During the attempted synthesis of the monoacetate ligand 5a an unusual reaction behaviour...
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Chiral metallocomplex synthons of α-amino acids. Synthesis, physical-chemical properties and applications
Popkov, Alexandr ; Lyčka, Antonín (advisor) ; Kotora, Martin (referee) ; Růžička, Aleš (referee) ; Pour, Milan (referee)
CONCLUSIONS Study of chiral amino acids synthons resulted in: I a deeper understanding of the intramolecular interactions affecting the stereochemistry of alkylation of the metallocomplex o_amino acids synthons. The interactions are a valuable tool for evaluation of the stereochemistry of the complexes; the disclosure of new phenomena in NMR spectroscopy (unexpected long-range couphngs.); 3 synthesis ofthe stereospecific synthon ofglycine; 4 the continuing development of diagnostic tools for the clinical diagnostic of some tumours. 5 the development of an envrronmentally_friendly procedure for multikilogram-scale preparatlon of starting metallocomplex chiral synthons ofo_amino acids.
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Study of transport properties of some polymer layers
Růžička, Aleš
This work studies various properties of polymer layers and hybrid layers containing inorganic nanoparticles. MEH-PPV and Polythiophene films are characterized by different experimental techniques. Dark J-V characteristics were measured at different temperatures and the mobility of holes was evaluated in a few cases. Photovoltage spectra are used for a determination of the exciton diffusion length and the SPV method is discussed. The influence of the inorganic nanoparticles CdS and ZnO incorporated into the polymer layers is studied by various experimental methods and the applications of these layers in the inorganic-organic hybrid solar cells are discussed. The inorganic nanoparticle size distributions are obtained by several experimental techniques and the results correspond with the assumptions.
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Chiral metallocomplex synthons of α-amino acids. Synthesis, physical-chemical properties and applications
Popkov, Alexandr ; Lyčka, Antonín (advisor) ; Kotora, Martin (referee) ; Růžička, Aleš (referee) ; Pour, Milan (referee)
CONCLUSIONS Study of chiral amino acids synthons resulted in: I a deeper understanding of the intramolecular interactions affecting the stereochemistry of alkylation of the metallocomplex o_amino acids synthons. The interactions are a valuable tool for evaluation of the stereochemistry of the complexes; the disclosure of new phenomena in NMR spectroscopy (unexpected long-range couphngs.); 3 synthesis ofthe stereospecific synthon ofglycine; 4 the continuing development of diagnostic tools for the clinical diagnostic of some tumours. 5 the development of an envrronmentally_friendly procedure for multikilogram-scale preparatlon of starting metallocomplex chiral synthons ofo_amino acids.
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Polycyclic tetraazamacrocycles
Plutnar, Jan ; Hermann, Petr (advisor) ; Podlaha, Jaroslav (referee) ; Růžička, Aleš (referee)
Two series of new bicyclic tetraazamacrorycles built up on skeletons of either 1,5,8,12-tetraazabiryclo[10.2.2]hexadecane (1,4-en-cyclam) I or 1,4,8,11- tetraazabicyclo[6.6.2]hexadecane (1,8-en-ryclam) 8 were prepared. The 1,4- en.cyc|am-based unsymmetrica| compounds bearing the pnitrobenzy| moieý (precursor for a biomolecule-conjugation) were synthesised exploiting the low so|ubi|iý of the intermediate quaternary derivative 2 in non-po|ar so|vents. The |igands 3 and 6 exhibited the expeďed comp|exing abi|ity towards copper(Il) and zinc(Il) although the complexation proceeded relatively slowly (at room temperature in order of hours). The mďa| comp|exes thus formed exhibited thermodynamic stability constants lower than those repofted for similar monoryclic tetraazamacrocycles (cyclam, Me+cyclam) probably due to inadvisability of the conformational change (chair or twisted-boat -> boat conformation of the piperazine subunit) conneďed to the metaI ion encapsulation. On the other hand, when the stability of coppe(Il) complex of 3 is compared to stabi|iý constant reported for the biryc|ic amine 1, the trend in the values of these constants is the same for the couple ligand I - ligand 3 as for the couple cyclam - Me+cyclam. During the attempted synthesis of the monoacetate ligand 5a an unusual reaction behaviour...
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Geminal bis(phosphinates)
David, Tomáš ; Lukeš, Ivan (advisor) ; Grüner, Bohumír (referee) ; Růžička, Aleš (referee)
Slow complexation is one of the major limitations of current macrocyclic chela- tors utilized in nuclear medicine for complexation of metal radionuclides. This property can be improved by ligand design. Among metal radioisotopes, the copper ones (e.g. 60Cu, 61Cu, 62Cu, 64Cu and 67Cu) have become commonly available in recent years and cyclam-derived ligands are the most suitable ligands for Cu2+ complexation. To alter the complexation rate, bis(phosphinic acid) group is promising unit as it is able to complex metal ions in acidic solu- tions. However, geminal bis(phosphinates) represent poorly studied group of compounds and, thus, it is challenging to uncover their properties. Several simple amino-bis(phosphinates) were synthesized and its acid-base and coordi- nation properties were studied. Unlike structurally similar geminal bis(phosphonates), the title compounds showed negligible adsorption onto hydroxyapatite (commonly used model of bone tissue). The obtained knowledge dealing with geminal bis(phosphinates) was utilized in synthe- sis of two novel cyclam derivatives. The ligands (bearing either one geminal bis(phosphinate) or one geminal phosphino-phosphonate pendant arm) were synthesized by highly efficient procedure. The corresponding Cu2+ complexes are formed with very high rates and show...
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