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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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Light platinum group metal complexes with a ferrocene N-phosphinoamide
Navrátil, Michal ; Štěpnička, Petr (advisor) ; Gyepes, Róbert (referee)
Title: Light platinum group metal complexes with a ferrocene N-phosphinoamide Author: Bc. Michal Navrátil Department: Department of Inorganic chemistry Supervisor: prof. RNDr. Petr Štěpnička, Ph.D., DSc. Abstract: The aim of this diploma thesis is the preparation of coordination compounds containing ferrocene phosphinoamide FcCONHPPh2 (1, Fc = ferrocenyl), whose preparation was discussed in author's bachelor thesis. Twelve new complexes are described in this thesis, including their characterisation by NMR and infrared spectroscopy, elemental analysis and mass spectrometry. In all cases the crystal structure was determined. Two palladium(II), one rhodium(III) and one ruthenium(II) precursors were used for the preparation of the complexes with each providing three new compounds. A reaction of the precursors with phosphinoamide 1 yielded complexes, in which the phosphinoamide was P-coordinated. This compound was a precursor for the other two complexes. The first one was obtained by a reaction with silver(I) perchlorate producing a cationic P,O-chelate. The other was obtained by a reaction with potassium tert-butoxide resulting in neutral P,O- chelate. All twelve complexes were prepared with optimised yields. Keywords: ferrocene, amides, phosphines, palladium, rhodium, ruthenium, structure elucidation.
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Theoretical studies of catalysts for Suzuki-Miyaura reaction
Měrka, Pavel ; Uhlík, Filip (advisor) ; Srnec, Martin (referee)
This thesis is focused on theoretical study of Suzuki-Miyaura cross- coupling reaction catalyzed by palladium complex with phosphinopherrocene li- gand. The aim of this work is to provide basic image of the catalytic cycle with newly prepared coordination compounds of palladium. Bromobenzene and phe- nyltriolborate were chosen as the model reagent. DFT method M06-2X was used for characterization of molecular goemetries of intermediates and most important transition states for all parts of catalytic cycle.
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Phosphinoferrocene ligands with polar amide substituents
Charvátová, Hana ; Štěpnička, Petr (advisor) ; Trávníček, Zdeněk (referee) ; Jambor, Roman (referee)
Title: Phosphinoferrocene ligands with polar amide substituents Author: Hana Charvátová Department: Department of Inorganic Chemistry Supervisor: prof. RNDr. Petr Štěpnička, Ph.D. Abstract: This thesis is focused on phosphino-urea ferrocene ligands that are still rather neglected in the literature. It describes the synthesis of novel polar amides and hydrazides of 1'-(diphenylphosphino)ferrocene-1-carboxylic acid (Hdpf) with or without ethylene linker bearing various urea and guanidine terminal functional groups. Urea and guanidine derivatives with ethylene bridge can be prepared from Hdpf and appropriate amine with amidation agents. Phosphine ureas without the linker are accessible from reactions of primary amide of Hdpf with suitable acylation agents while analogical guanidine is obtained from guanylation of amide-amine generated from Hdpf acylbenzotriazole and ethylenediamine. Reaction of the acylbenzotriazole with free guanidine leads to [1-(diphenylphosphino)ferrocenecarbonyl]guanidine hydrochloride. These ferrocene ligands were used to prepare four types of palladium(II) complexes, viz. where L denotes the newly synthesized ligands and LNC is 2- [(dimethylamino)methyl]phenyl-C,N auxiliary chelating ligand. Catalytic efficiency of complexes with ethylene bridge was tested on reactions of aromatic...
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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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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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Synthesis and properties of a ferrocenyl-substituted diphosphine
Verníček, Marek ; Štěpnička, Petr (advisor) ; Vojtíšek, Pavel (referee)
Title: Synthesis and properties of a ferrocenyl-substituted diphosphine Author: Marek Verníček Department: Department of Inorganic Chemistry (Faculty of Science, Charles University in Prague) Supervisor: prof. RNDr. Petr Štěpnička, Ph.D. In this work, a new ligand was prepared, namely N,N-bis[2-(difenylfosfino)ethyl]amide of ferrocenecarboxylic acid. This ligand was obtained by the reaction of pentafluorophenylferrocenecarboxylate, which was newly synthesized, with the appropriate amine. The ligand was characterized by 1 H, 13 C, 31 P NMR spectroscopy, elemental analysis, IR spectroscopy and by mass spectrometry. Subsequently, a sulphide was prepared from this diphosphine-amide by the reaction with sulfur in toluene at elevated temperature. The sulphide was characterized in the same manner and also analyzed by single-crystal X-ray diffraction analysis. The coordination properties of the ligand were examined in a reaction with [PtCl2(cod)] (cod = cyclooctadiene) in dichloromethane. The resulting complex was studied by 1 H NMR, mass spectrometry, elemental analysis and by X-ray structural analysis. Keywords: ferrocene; phosphine ligands; amidophosphines; platinum(II) complexes; crystal structure.
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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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