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Synthesis and characterization of bidentate P,N-donor ferrocene ligand
Rezazgui, David ; Schulz, Jiří (advisor) ; Hulla, Martin (referee)
Title: Synthesis and characterization of bidentate P,N-donor ferrocene ligand Author: Bc. David Rezazgui Department: Department of Inorganic chemistry Supervisor: RNDr. Jiří Schulz, Ph.D. The main goal of this thesis was the preparation and characterization of ferrocene ligand 4-[1'-(diphenylphosphino)ferrocen-1-yl]morpholine (compound 3). Compared to structurally similar compounds, compound 3 offers greater geometrical flexibility which might have a positive effect in some applications, for example in catalysis by transition metal complexes. Two new compounds were synthesized along the synthetic route of phosphinoamine 3, the protected amine 1 and morpholine derivate 2. Selenide 4 was prepared in order to determine the basicity of compound 3 via the direct scalar interaction of 77 Se with 31 P. The synthesis comprised phosphinylation of 1,1'-dibromoferrocene, protection of the obtained 1-bromo-1'- (diphenylphosphino)ferrocene with sulfur, azidation and immediate reduction to protected amine 1. Morpholine derivate 2 was subsequently synthesized by cyclization reaction with bis(2-chloroethyl)ether. Phosphinoamine 3 was obtained by deprotection of compound 2 with Raney nickel. Finally, selenide 4 was obtained by the reaction of 3 with KSeCN. All newly prepared compounds were analyzed by NMR and transmission...
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Catalytic Cycloaddition Reactions of Tribenzocyclyne
Jacko, Jaroslav ; Kotora, Martin (advisor) ; Schulz, Jiří (referee)
The main aim of the bachelor thesis was to investigate the reactivity of tribenzocyclyne, a triangular molecule, undergoing reactions with antiaromatic biphenylenes and their heteroanalogues. Those reactions consist of C-C activations of strained bond mediated by the complexes of the group 9 elements, followed by migratory insertion of present alkyne which leads to the formation of a substituted aromatic ring. Presented method facilitated the setting of a experiment as well as cutting down on reaction steps. These investigations will subsequently serve for further progress in the chemistry of cyclic hexa- ortho-phenylenes. Key words: catalysis, cycloaddition, tribenzocyclyne, the C-C bond cleavage
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Coordination properties of TACN ethylphosphonic derivative
Poláková, Zuzana ; Kubíček, Vojtěch (advisor) ; Schulz, Jiří (referee)
Ligand NOTPOEt was synthesized. Protonation constants and stability constants of Cu(II), Zn(II), Ni(II) and Ga(III) complexes were determined by potentiometric titrations. Cu(II) complex was characterized by UV-VIS spectroscopy and formation of Ga(III) complex was studied by NMR spectroscopy. The work was aimed at characterisation of the ligand with respect to potential application in biomedical imaging techniques.
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Polar ligands derived from a phosphinoferrocene hydrazide
Vašíček, Tomáš ; Štěpnička, Petr (advisor) ; Schulz, Jiří (referee)
Title: Polar ligands derived from a phosphinoferrocene hydrazide Author: Tomáš Vašíček Institution: Faculty of Science, Charles University in Prague, Department of Inorganic Chemistry Supervisor: prof. RNDr. Petr Štěpnička, Ph.D. This thesis describes the syntheses of three new ligands derived from a phosphinoferrocene hydrazide, namely 1'-(diphenylphosphino)ferrocene-1-carbohydrazide. The reaction conditions were optimized by varying the reaction time and temperature in order to achieve high yields and purity of the products. Newly prepared compounds that bear extended polar groups were characterized by NMR spectroscopy, mass spectrometry, infrared spectroscopy and by elemental analysis. Additionally, the molecular structure of 1'-(diphenylphosphino)-1- {[2-(aminocarbonyl)hydrazino]-carbonyl}ferrocene (8) was determined by X-ray diffraction analysis. Key words: Ferrocene, Phosphines, Hydrazides
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Polar ferrocene amidophosphines for catalytic applications
Schulz, Jiří ; Štěpnička, Petr (advisor) ; Růžička, Aleš (referee) ; Čermák, Jan (referee)
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...
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Synthesis of phosphinic acids
Kruliš, Tomáš ; Kubíček, Vojtěch (advisor) ; Schulz, Jiří (referee)
Two types of phosphinic acids were prepared: N,N-bis(carboxymethyl)aminomethyl phosphinic acid and carboxyethylphosphinic acid. Afterwards they were used to synthesize bisphosphinic acids: 1-hydroxy-ethan-1,1-bis[N,N-bis(carboxymethyl)aminomethyl phosphinic] acid and 1-hydroxy-ethan-1,1-bis(carboxyethyl)phosphinic acid. All compounds were characterized by NMR and mass spectroscopy. N,N-bis(carboxymethyl)aminomethylphosphinic acid was synthesized by Mannich type reaction. Carboxyethylphosphinic acid was prepared by alkylation of bis(trimethylsilyloxy)phosphine. Both bisphosphinic acids were prepared by reaction of silylesters of phosphinic acids with acetylchloride. All compounds were prepared in moderate or good yields. Keywords: Organophosphorus synthesis, phosphinic acids, bisphosphinic acids
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Polar ferrocen phosphinoamides
Schulz, Jiří
v anglickém jazyce Polar ferrocene phosphinoamides Polar phosphane-carboxamides 1-(diphenylphosphanyl)-1-[N-(2-hydroxyethyl)carba- moyl]ferrocene (4) and 1-(diphenylphosphanyl)-1-[N,N-bis(2-hydroxyethyl)carbamoyl] ferrocene (5) bearing hydroxyethyl pendants derived from 1-(diphenylphosphanyl)-1- ferrocene-carboxylic acid (Hdpf) were synthesized either by direct amidation or via active pentafluophenyl ester (3). Reactions of 4 and 5 with [PdCl2(cod)] (cod = 2 :2 -cyclocta-1,5- diene) afforded the respective bis(phosphane) complexes trans-[PdCl2L2] (6, L = 4; 7, L = 5). Depending on the solvent used in their subsequent crystallisation (ethanol or chloroform), the complexes were isolated as distinct solvatomorphs. All new compounds have been characterised by spectral methods and by X-ray crystallography. The structure determination for both ligands and solvated complexes (62EtOH, 66CHCl3, 72EtOH, and 74CHCl3) revealed the dominating role of hydrogen bond interactions in their solid-state assemblies. The nature and complexity of the hydrogen bonded arrays changed broadly along with the ligand structure (one vs. two 2-hydroxy-ethyl chains) and their number in the discrete species (free ligand vs. the complexes), and also with the solvent properties. Catalytic tests performed with 6 and 7 on...
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Bis(phosphinates)
Křečková, Pavlína ; Kubíček, Vojtěch (advisor) ; Schulz, Jiří (referee)
Title: Bis(phosphinates) Autor: Pavlína Křečková Department: Department of Inorganic Chemistry, Faculty of Science Supervisor: RNDr. Vojtěch Kubíček, Ph.D. Supervisor's e-mail address: kubicek@natur.cuni.cz Abstract Four geminal bis(phosphinate) acids were prepared and characterized by TLC, NMR, MS, EA. The compounds were acquired in high yields (over 55 %). Stability of these compounds was tested in chosen aqueous buffers, which covered a wide range of pH. The experiments showed that the prepared compounds are not fully stable. Performed experiments have shown negligible sorption of synthesized bis(phosphic) acids to hydroxyapatite, which was used as a model of bone tissue. Keywords: geminal, bis(phosphinate), decomposition, sorption.
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