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Electronically dissymmetric ferrocene bisphosphines
Horký, Filip
This Thesis describes the synthesis, reactivity, coordination properties, and catalytic activity of novel electronically dissymmetric bisphosphines structurally related to 1,1'-bis(diphenylphosphino)ferrocene (dppf). First, a methylene spaced congener containing a primary phosphine group, which is stable in the air, Ph2PfcCH2PH2 (fc = ferrocene-1,1'-diyl), was prepared. While studying its reactivity, an unprecedented stable primary phosphine oxide, Ph2PfcCH2P(O)H2, was isolated. The primary phosphine, the corresponding phosphine oxide, dppf and the known bis-tertiary phosphine Ph2PfcCH2PPh2 were studied as ligands in Ru(II) complexes. The catalytic activity of the defined complexes was compared in two ruthenium-catalyzed reactions: cyclization of (Z)-3-methylpent-2-en-4-yn-1-ol into 2,3-dimethylfuran and isomerization of estragole to anethole. Second, the remarkable stability of the prepared primary phosphine oxide called for a detailed investigation of this poorly described class of compounds. As a result, stable primary phosphine chalcogenides lacking steric protection FcCH2P(Y)H2 (Fc = ferrocenyl; Y = O, S, Se) were isolated for the first time. These compounds were studied as ligands in reactions with hard and soft Lewis acids (Zn(II) and Ru(II)), and the reactivity of the P-H hydrogens was...
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Electronically dissymmetric ferrocene bisphosphines
Horký, Filip ; Štěpnička, Petr (advisor) ; Horáček, Michal (referee) ; Šebesta, Radovan (referee)
This Thesis describes the synthesis, reactivity, coordination properties, and catalytic activity of novel electronically dissymmetric bisphosphines structurally related to 1,1'-bis(diphenylphosphino)ferrocene (dppf). First, a methylene spaced congener containing a primary phosphine group, which is stable in the air, Ph2PfcCH2PH2 (fc = ferrocene-1,1'-diyl), was prepared. While studying its reactivity, an unprecedented stable primary phosphine oxide, Ph2PfcCH2P(O)H2, was isolated. The primary phosphine, the corresponding phosphine oxide, dppf and the known bis-tertiary phosphine Ph2PfcCH2PPh2 were studied as ligands in Ru(II) complexes. The catalytic activity of the defined complexes was compared in two ruthenium-catalyzed reactions: cyclization of (Z)-3-methylpent-2-en-4-yn-1-ol into 2,3-dimethylfuran and isomerization of estragole to anethole. Second, the remarkable stability of the prepared primary phosphine oxide called for a detailed investigation of this poorly described class of compounds. As a result, stable primary phosphine chalcogenides lacking steric protection FcCH2P(Y)H2 (Fc = ferrocenyl; Y = O, S, Se) were isolated for the first time. These compounds were studied as ligands in reactions with hard and soft Lewis acids (Zn(II) and Ru(II)), and the reactivity of the P-H hydrogens was...
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Interoperability of compiled PHP framework with .NET environment and package management
Horký, Filip ; Husák, Robert (advisor) ; Kofroň, Jan (referee)
PHP language has been dominating the web development industry for a long time now. Each major PHP framework brings together a large community and a solid codebase, providing features and tools that make the PHP web application devel- opment even simpler. Joining this vast world with .NET is an aim of Peachpie, PHP compiler to .NET. This provides means to use Symfony framework in .NET, yielding advantages for both the PHP developers striving for more security and the .NET programmers lacking third-party content. Doing so with plain Peachpie compiler, however, brings problem of actual usability of the features Symfony pro- vides. Each project would require to recompile Symfony Components again and thus result in both time overhead and tedious manual configuration. This thesis shows it is possible to improve this process and enable intuitive usage of Sym- fony framework in the .NET environment. It denotes utilities for semi-automatic compilation of the Symfony Components into the NuGet packages and migration of simple Symfony applications to .NET. Furthermore, it provides tools for ad- ditional interoperability between Twig and Razor template engines, and a set of examples of its actual usage.
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Copper(I) complexes with phosphinonitrile donors
Horký, Filip ; Štěpnička, Petr (advisor) ; Kubíček, Vojtěch (referee)
Title: Copper(I) complexes with phosphinonitrile donors Author: Bc. Filip Horký Department: Department of Inorganic chemistry Supervisor: prof. RNDr. Petr Štěpnička, Ph.D. Abstract: Although coordination compounds with phosphinonitrile ligands are already well known, in the vast majority of these complexes these ligands coordinate as simple P-donors with their cyano groups acting as auxiliary substituents. This led us to synthesize and study a series of Cu(I) complexes with two isomeric phosphinonitrile donors, namely 2-(diphenylphosphino)benzonitrile (Lo ) and 2-(diphenylphosphino)benzonitrile (Lp ), with different ligand-to-metal ratios and possibly characterize further coordination modes offered by these hybrid donors. This work describes the preparation of phosphinonitrile complexes from the aforementioned ligands and simple copper(I) halides (CuX, X = Cl, Br, I), pseudohalides (X = CN) and from [Cu(MeCN)4][BF4]. The products were characterized by nuclear magnetic resonance, infrared spectroscopy and elemental analysis, mass spectrometry, and their solid-state structures were determined by single-crystal X-ray crystallography. In addition, luminescent properties of the Cu(I) complexes were studied and catalytic activity of selected complexes was tested in copper-catalyzed alkyne-azide cycloaddition...
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Synthesis and characterization of ferrocenylated amidophosphine
Horký, Filip ; Štěpnička, Petr (advisor) ; Kubíček, Vojtěch (referee)
Title: Synthesis and characterization of ferrocenylated amidophosphine. Author: Filip Horký Department: Department of Inorganic chemistry Supervisor: prof. RNDr. Petr Štěpnička, Ph.D. Abstract: Complexes with amidophosphine donors have found interesting applications in catalysis and in medicinal chemistry. This led us to synthesize {[(2-(diphenylphosphino) ethyl)]-amino]carbonyl}ferrocene (compound 1) and the corresponding phosphine oxide (compound 2). This work describes three new synthetic routes to the target amidophosphine 1. The first one is a simple reaction of ferrocenecarboxylic acid with 2-(diphenylphosphino)ethylamine with reagents mediating amide bond formation. The second approach is based on the reaction of the mentioned amine with the respective acylbenzotriazole. Finally, the third way makes use of the reaction between the amine and an active ester, pentafluorophenyl ferrocencarboxylate. All products and intermediates were characterized by NMR spectra. The newly prepared phosphine oxide 2 was further characterized by infrared spectroscopy, elemental analysis, mass spectrometry and its crystal structure was determined by single-crystal X-ray crystallography. Keywords: ferrocene ligands, ferrocene, phosphine, amide, phosphineoxide, synthesis.
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