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Electrochemical Characterization of Molecular Conductors Containing Redox Switching Element
Nováková Lachmanová, Štěpánka ; Vavrek, František ; Sebechlebská, Táňa ; Šebera, Jakub ; Kolivoška, Viliam ; Lukášek, J. ; Balzer, N. ; Valášek, M. ; Mayor, M. ; Hromadová, Magdaléna
Electrochemical properties of new molecules containing tripodal anchor and redox switching\nelement have been studied by cyclic voltammetry and DFT quantum mechanical calculations.\nComparison of their redox properties with individual organometallic [Ru(terpy)2]2+t3+ and\n[Os(terpy)2]2+t3+ redox centers shows that covalently bonded tripodal anchor does not\ncompromise the reversibility of a redox process and has no effect on the stability of new\nmolecules. New molecular conductors have smaller HOMO-LUMO gap and both are oxidized\nat only slightly more positive potentials after tripodal substitution making them suitable for the\ndevelopment of molecular conductors with switching abilities.
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Effect of silver in homogeneous gold catalysis
Motloch, Petr ; Roithová, Jana (advisor) ; Hocek, Michal (referee)
Gold catalysis has recently experienced a sustained upswing in interest from scientific community. The amount of new reactions catalysed by gold is so significant that little is known about mechanisms of most of these reactions. Research into mechanisms of (not only) gold catalysed reactions is therefore very significant area of interest and important to the continued improvement of gold catalysed reactions. Formation of cationic π-complexes is considered a first mechanistic step in reactions catalysed by gold(I). The bond dissociation energies of gas phase cationic π-complexes were investigated by mass spectrometry and theory calculations in this thesis. These complexes consisted of differently substituted unsaturated hydrocarbons (alkenes, alkynes, alkadienes and allenes) and complex cations of silver and gold containing second ligand (triphenylphosphine, acetonitrile). On the basis of the results obtained from this study, a possible origin of the "silver effect" in gold(I) catalysis is discussed. Key words catalysis, gold, silver, mass spectrometry, DFT calculations, reaction intermediates
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Direct monitoring of metal-catalyzed reactions using electrospray ionization mass spectrometry
Tsybizova, Alexandra ; Roithová, Jana (advisor) ; Jahn, Ullrich (referee) ; Kvíčala, Jaroslav (referee)
The current dissertation thesis is focused on the investigation of metal-catalyzed reactions using electrospray ionization mass spectrometry as the primary research technique. However, other gas- phase methods such as tandem mass spectrometry, infrared multiphoton dissociation spectroscopy and quantum chemical calculations have also been involved to unravel and support the findings and proposals. As organometallic chemistry is a very broad and complicated topic, this thesis is only focused on a few projects. The fist of them is dedicated to copper acetate speciation in organic solvents, the second - to the mechanistic investigation of copper catalyzed aerobic cross coupling of thiol esters and arylboronic acids, the third studied coordination and bond activation of nickel(II) - phenylpyridine complexes and the last investigated carboxylate assisted C-H activation reactions.
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Effect of silver in homogeneous gold catalysis
Motloch, Petr ; Roithová, Jana (advisor) ; Hocek, Michal (referee)
Gold catalysis has recently experienced a sustained upswing in interest from scientific community. The amount of new reactions catalysed by gold is so significant that little is known about mechanisms of most of these reactions. Research into mechanisms of (not only) gold catalysed reactions is therefore very significant area of interest and important to the continued improvement of gold catalysed reactions. Formation of cationic π-complexes is considered a first mechanistic step in reactions catalysed by gold(I). The bond dissociation energies of gas phase cationic π-complexes were investigated by mass spectrometry and theory calculations in this thesis. These complexes consisted of differently substituted unsaturated hydrocarbons (alkenes, alkynes, alkadienes and allenes) and complex cations of silver and gold containing second ligand (triphenylphosphine, acetonitrile). On the basis of the results obtained from this study, a possible origin of the "silver effect" in gold(I) catalysis is discussed. Key words catalysis, gold, silver, mass spectrometry, DFT calculations, reaction intermediates
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Properties of bipyridine N,N'-dioxides in the gas phase
Ducháčková, Lucie ; Kotora, Martin (referee) ; Roithová, Jana (advisor)
Lucie Ducháčková Bipyridine N,N'-dioxides are organocatalysts, which are used as a chiral Lewis bases in enantioselective catalysis. The aim of this diploma thesis was systematic investigation of the proton affinities of bipyridine N,N'-dioxide derivatives. Further, the complexation properties and chiral recognition in the gas phase of bipyridine N,N'-dioxide derivatives were examined. Mass spectrometry complemented with infrared multiphoton dissociation spectroscopy and quantum-chemistry calculations using the density functional theory (DFT) were used as the main experimental methods. Bipyridine N,N'-dioxides are a new class of oxygen superbases with proton affinities larger than 1030 kJ/mol. Complexation properties and reactivities of their metal complexes are comparable to 2,2'-bipyridine.
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