National Repository of Grey Literature 24 records found  1 - 10nextend  jump to record: Search took 0.00 seconds. 
Homologous ferrocene phosphines
Vosáhlo, Petr
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.
Light platinum group metal complexes with a ferrocene N-phosphinoamide
Navrátil, Michal
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.
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...
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.
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.
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.
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.
Synthesis and catalytic properties of phosphinoferrocene guanidine
Bárta, Ondřej ; Štěpnička, Petr (advisor) ; Vojtíšek, Pavel (referee)
Title: Synthesis and catalytic properties of phosphinoferrocene guanidine Author: Ondřej Bárta Institution: Faculty of Science, Charles University in Prague, Department of Inorganic Chemistry Supervisor: prof. RNDr. Petr Štěpnička, Ph.D. Polar phosphine ligands proved to be useful in homogeneous and biphasic catalysis. Most of these phosphines bears anionic functional groups. On the other hand, functionalization of phosphines by cationic substituents is still quite uncommon, although these functional groups possess properties that could improve catalytic performance of the catalyst. In this regard, nitrogenous bases are particularly attractive due to their inherent basicity and the ability to enter into hydrogen bonding interactions. This thesis describes the synthesis of a novel ferrocene-based phosphine functionalized with guanidine moiety, viz. N-[1′-(diphenylphosphino)ferrocenylmethyl]guanidine (3). This compound was obtained by direct guanylation of 1′-(diphenylphosphino)- 1-(aminomethyl)ferrocene (2) (see scheme). Compound 3 was further used to prepare palladium complexes including the unusual zwitterionic complex [PdCl3(3H)]. The molecular structures of the prepared complexes were determined by X-ray diffraction analysis. Catalytic properties of phosphine 3 and complex [PdCl3(3H)] were...
Functional phosphinoferrocene ligands
Škoch, Karel ; Štěpnička, Petr (advisor) ; Grüner, Bohumír (referee) ; Dostál, Libor (referee)
6 Abstract The first part of this Thesis describes the preparation of a novel phosphanyl-ferrocene amine, Ph2PfcCH2NH2 (1; fc = 1,1'-ferrocendiyl) in two steps from the known aldehyde Ph2PfcCHO. An oxime Ph2PfcCH=NHOH was prepared firstly by a condensation reaction, and subsequently treated with Li[AlH4] to give the desired amine. The amine was converted into its more stable hydrochloride salt, Ph2PfcCH2NH3Cl. Derivatization of amine 1 was examined through the preparation of a series of phosphanyl-urea ligands Ph2PfcCH2NHC(E)NR1 R2 . Some of these compounds were also prepared via an alternative method employing reductive amination reaction. These donors and their Pd(II) complexes were evaluated in Pd-catalyzed reaction of arylbromides with K4[Fe(CN)6] in order to prepare corresponding benzonitrile derivatives using aqueous reaction solvents. The reaction proceeds with excellent yields and purity when 1 mol.% of Pd- catalyst is used (at 100 řC for 3 hours), especially for electron-rich bromobenzenes. Substrates with electron-withdrawing substituents react significantly slower and corresponding hydrolytic products (benzamides) are isolated. The coordination properties of phosphanyl-amine 1 were examined towards Cu(I) ions. Thus, reaction of 1 with [Cu(MeCN)4][BF4] provided bis-chelate complex [Cu(1- κ2...

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