|
|
The Study of hydration models on platinum complexes important in anticancer cure
Bradáč, Ondřej ; Burda, Jaroslav (advisor) ; Záliš, Stanislav (referee)
In this work, there are studied some biologically important platinum complexes, cisplatin analogues, with central platinum atom in state Pt(II), or Pt(IV). I concentrated on the hydration processes of the examined complexes. Thermodynamical and kinetical aspects of reactions were studied and NPA charge analyses were carried out, too. All computations were performed on DFT level with B3LYP functional. All reactions were considered in vacuum. Supermolecular approach was used for energy calculations.
|
|
|
Theoretical study of spin-orbit coupling on spectra and photophysics of rhenium complexes
Heydová, Radka ; Záliš, Stanislav (advisor) ; Slavíček, Petr (referee) ; Srnec, Martin (referee)
Title: Theoretical study of spin-orbit coupling on spectra and photophysics of rhenium complexes Author: RNDr. Radka Heydová Department: Physical and Macromolecular Chemistry Supervisor: Ing. Stanislav Záliš, CSc., JHI AS CR, v.v.i. Supervisor's e-mail address: stanislav.zalis@jh.inst-cas.cz Abstract: Relativistic effects, especially spin-orbit coupling (SOC), play an essential role in transition metal chemistry and SOC treatment is indispensable for a correct theoretical description. To demonstrate the importance of SOC, the energies and oscillator strengths of vertical transitions for a series of [ReX(CO)3(2,2'-bipyridine)] (X = Cl, Br, I) and [Re(imidazole)(CO)3(1,10-phenanthroline)]+ complexes were calculated in the spin-free (SF) and spin-orbit (SO) conceptual frameworks. Two different computational approaches were adopted: SO-MS-CASPT2 where SOC was added a posteriori using a configuration interaction model (SO-RASSI), and the approximate perturbative SO-TD-DFT method. Relativistic effects were included via the two-component Douglas-Kroll-Hess transformation and the zeroth-order regular approximation in the former and the latter technique, respectively. The SF (i.e. accounting only for the scalar relativistic effects) and SO results from both methods were compared with each other and to available...
|
|
|
The theoretical exploration of the interactions of dirhodium complexes.
Kovaľ, Tomáš ; Burda, Jaroslav (advisor) ; Záliš, Stanislav (referee)
This work focuses on the study of interactions of the Diaqua-tetrakis(-acetylato)dirhodium(II,II) complex. This complex belongs to compounds of transition metals, which show activity in anticancer treatment. In this work, the interactions of this complex with ammonia and guanine are studied. The interactions with ammonia are represented by a replacement reaction of oxygen from acetyl ligand or aqua ligand. Another reaction is the replacement of water bonded to rhodium by guanine. Guanine can form a bond to rhodium with oxygen O6 or nitrogen N7. Optimization of the structures are made at the DFT level with 6-31G* basis set. For reactions with ammonia transition states were found. NPA charge analyses, thermodynamical and kinetical analyses were performed. All these analyses were done at the DFT level with aug-cc-pvdz basis set. To describe the electronic structure of rhodium atoms pseudopotentials and pseudobasis were used. All calculations were modeled in gas phase.
|
|
|
The Study of hydration models on platinum complexes important in anticancer cure
Bradáč, Ondřej ; Burda, Jaroslav (advisor) ; Záliš, Stanislav (referee)
In this work, there are studied some biologically important platinum complexes, cisplatin analogues, with central platinum atom in state Pt(II), or Pt(IV). I concentrated on the hydration processes of the examined complexes. Thermodynamical and kinetical aspects of reactions were studied and NPA charge analyses were carried out, too. All computations were performed on DFT level with B3LYP functional. All reactions were considered in vacuum. Supermolecular approach was used for energy calculations.
|
|
| |
|
|
Modelování spektrálních a fotochemických vlastností diiminových karbonylových komplexů přechodových kovů s diiminy
Šebera, Jakub ; Záliš, Stanislav ; Vlček, Antonín
The felxibility pf the coordination sphere of mixed valence carbonyl complexes enables to tune spectral and protochemical properties. The variety of excited states in ilustrated on Ru, Re and W mixed ligand carbonyl complexed. The lowest excited states of [W(CO)4L] and [W(CO)5L’] (L=N,N'-di-methyl-1,4-diazabutadiene, ethylenediamine, 2,2’-bipyridine, phenantroline; L’= pyridine, 4-CN-pyridine, piperidine) ckomplexes were found to be either W -> pi*(L) or W -> pi*(CO) in charakter, depending on the type of the heteroligands.
|
guest ::
