Inorganic Chemistry Commons^™

Synthesis And Thermodynamic Analysis Of Volatile Beta-Diketone Complexes Of Select Lanthanides Via Gas-Phase Separations, Daniel Hanson

Doctoral Dissertations

Rapid separation techniques for fission and activation products have long been desired to supplant the slow solution-based methodologies currently used. In this work, rare earth elements were derivatized with β [beta]-diketones to synthesize rare earth complexes with high volatility suitable for gas-phase separations. Rare earth elements samarium and dysprosium were combined with hfac (1,1,1,5,5,5-hexafluoro-2,4-pentadione) and fod (6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione) and analyzed using a gas-phase separation technique. Rare earth elements praseodymium and europium were combined with dpm (2,2,6,6-tetra-methyl-3,5-heptanedione) and similarly analyzed. Employing the data from the separations, the entropy (Δ [delta] S) and enthalpy (Δ [delta] H) of adsorption were evaluated mathematically based …

Synthesizing Strong Donor Macrocyclic Tetracarbene Metal Complexes For Catalytic Aziridination, Steven Alan Cramer

Doctoral Dissertations

A small ringed macrocyclic tetracarbene ligand was developed due to the inherent ability of N-heterocyclic carbenes (NHCs) to stabilize high oxidation states of transition metals. This new strong donor ligand was prepared by first synthesizing an 18-atom ringed macrocyclic tetraimidazolium ligand precursor. The tetraimidazolium can be prepared by a two-step procedure. This ligand precursor was deprotonated to prepare a monomeric platinum tetracarbene complex.

A new iron macrocyclic tetra-carbene complex was synthesized by an in situ strong base deprotonation strategy of the ligand precursor. The iron tetracarbene complex was found to catalyze the aziridination of a wide array of functionalized aryl …

Double-Hinged Di-1,2,4-Triazoles For Synthesis Of Breathing Mofs, Christopher Ray Murdock

Doctoral Dissertations

Employing semi-rigid di-1,2,4-triazoles as ligands has led to the formation of a plethora of Metal-Organic Framework (MOF) architectures. The ability for the ligands to exhibit multiple conformations through a “hinge” effect allows for the formation of a multitude of MOF topologies and dimensionalities. Employment of a di-triazole containing a central trans-butene moiety was initially studied and led to the formation of two three-dimensional copper MOFs. The frameworks can be synthesized independently, but a reaction occurs in water wherein the kinetic product is used as a reagent to synthesize the topologically distinct thermodynamic product.

Additional testing of reaction conditions with …