Ligand influences on properties of uranium coordination complexes. Structure, reactivity, and spectroscopy

In this thesis several different aspects of uranium chemistry are presented. It was shown that terminal uranium(V) oxo and imido complexes [((RArO)3tacn)UV(O)] and [((RArO)3tacn)UV(NSiMe3)] (R = t Bu, Ad) can be oxidized by silver(I) hexafluoro-antimonate to the uranium(VI) oxo and imido complexes [((RArO)3tacn)UVI(O)]SbF6 and [((RArO)3tacn)UVI(NSiMe3)]SbF6. While for the t Bu-derivative of the oxo complex an equatorial coordination is observed due to stabilization by the inverse trans-influence, normal axial coordination is observed for the Ad-derivative and both imido complexes. The inverse trans-influence was thus proven to be a key factor for the coordination mode of a terminal ligand on high valent uranium complexes. LIII XANES was shown to be a great tool for the determination of oxidation states of uranium complexes. Therefore, a series of uranium complexes in all stable oxidation states for uranium, +III to +VI was prepared, and their spectra analyzed. All compounds bear only O-donor ligands in addition to the chlating trisaryloxide-tacn-ligand. A separation of 1.5 to 3 eV in the white line energy is observed between the different oxidation states. This series can be used as reference for compounds, where oxidation state assignment is not obvious, such as a ketyl radical complex [((t-BuAr)O3tacn)U(O-C(t-BuPh)2.-)]. For this complex, the oxidation state of +IV could be assigned. Moreover, a series of isostructural uranium(IV) complexes was prepared. The influence of different ligands according to the spectrochemical series on the electronic and magnetic properties could be shown using UV/vis/NIR spectroscopy and variable temperature SQUID measurements. Calculations of uranium LIII XANES spectra show a variation in the shape of the spectra and thus high resolution PFY-XANES would be a great tool to determine the electronic influence of these different axial ligands. Using the single N-anchored ligand system, the first example of a uranium(IV) μ-trithiocarbonate was synthesized and characterized. Reaction of the μ-sulfide complex [{((AdArO)3N)UIV}2(μ-S)], which is obtained by reaction of the uranium(III) complex with triphenylphosphine sulfide, with CS2 leads to the formation of the [{((AdArO)3N)UIV}2(μ-κ2:κ2-CS3)]. The coordination mode of the trithicarbonate differes from that of the respective carbonate, obtained previously from a similar reaction of the μ-oxo complex with CO2. With the help of detailed DFT calculations, the different reactivity of uranium(III) towards CO2 and CS2 is rationalized. Finally, a series of the first uranium vinyl complexes is presented. These are obtained through inter- and intramolecular C-C-coupling reactions of terminal mono- or bisalkynes on a uranium(III) complex. Detailed mechanistic DFT calculations show that a bimetallic mechanism is energetically most likely. This mechanism can be transferred to the catalytic alkyne coupling using both uranium(III), as reported by Eisen in the late 90's, and also transition metal catalyzed C-C-coupling, where a bimetallic mechanism should be taken into account.