<p> β-Diketones are well known to form metal complexes with practically every known metal and metalloid. Metal complexes of fluorinated β-diketones generally exhibit increased volatility and thermal stability compared to the non-fluorinated analogues, and thus are used extensively in various chemical vapor deposition (CVD) processes for the deposition of metal, simple or mixed metal oxides, and fluorine-doped metal oxide thin films. Furthermore, the electron-withdrawing nature of the fluorinated ligand enhances the Lewis acidity of a coordinatively unsaturated metal center which facilitates additional coordination reactions. The physical and structural properties of fluorinated β-diketonate complexes are discussed in Chapter 1 and a few key application examples are given.</p><p> The focus of this work is the synthesis and single crystal X-ray structural characterization of unsolvated and coordinatively unsaturated metal complexes of bis(pentafluorobenzoyl)- methanide (L, C<sub>6</sub>F<sub>5</sub>COCHCOC<sub> 6</sub>F<sub>5</sub><sup>-</sup>). In Chapter 2, we present the preparation and isolation of the unsolvated complex [Cu(L)<sub>2</sub>] in pure crystalline form for the first time. We subsequently investigated the reaction of unsolvated [Cu(L)<sub>2</sub>] with sodium hexafluoroacetylacetonate [Na(hfac)] in a solvent-free environment. This reaction allowed the isolation of the first heterometallic Na–Cu diketonate [Na<sub>2</sub>Cu<sub>2</sub>(L)<sub> 4</sub>(hfac)<sub>2</sub>] structurally characterized by single crystal X-ray crystallography. Thermal decomposition of [Na<sub>2</sub>Cu<sub>2</sub>(L)<sub> 4</sub>(hfac)<sub>2</sub>] was investigated for its potential application in MOCVD processes. In the final chapter, we present the first exploration of the anhydrous synthesis of Co(II) complexed with bis(pentafluorobenzoyl)methanide in order to produce a complex without ligated water. Single crystal X-ray crystallographic investigations revealed the isolation of the ethanol adduct, [Co<sub>2</sub>(L)<sub>4</sub>(C<sub>2</sub>H<sub>5</sub>OH)<sub>2</sub>], and following the removal of ethanol, a 1,4-dioxane adduct, [{Co<sub> 2</sub>(L)<sub>4</sub>}<sub>2</sub>(C<sub>4</sub>H<sub>8</sub>O<sub>2</sub>)]. </p><p> In this work, we have provided the first investigation of the synthesis, isolation and single crystal X-ray structural characterization of unsolvated and coordinatively unsaturated Cu(II) and Co(II) complexes of bis(pentafluorobenzoyl)methanide ligand. These studies demonstrate how the electrophilicity of a coordinatively unsaturated metal complexed to highly-fluorinated â-diketone ligands can be utilized for the formation of new adducts or new and interesting heterometallic complexes. This body of work provides a basis upon which future research into unsolvated and unligated bis(pentafluorobenzoyl)methanide metal complexes can expand.</p><p>
| Identifer | oai:union.ndltd.org:PROQUEST/oai:pqdtoai.proquest.com:10680674 |
| Date | 12 December 2017 |
| Creators | Crowder, Janell M. |
| Publisher | State University of New York at Albany |
| Source Sets | ProQuest.com |
| Language | English |
| Detected Language | English |
| Type | thesis |
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