This thesis describes the synthesis, structure and reactivity of singly bridged dinuclear Group 11 metal complexes, supported by N-heterocyclic carbene (NHC) ligands. These complexes include dinuclear copper(I) complexes that demonstrate three-center, two-electron bonding with short intermetallic distances. In the first part of this study, a hydride-bridged dicopper cation, {[(IDipp)Cu]2(μ-H)}+ BF4–, which adopts a bent arrangement about the hydride was isolated. It undergoes facile methanolysis, readily reacts with carbon dioxide to afford a (κ2-formate)-bridged dicopper species, and coordinates carbon monoxide reversibly to form a carbonyl adduct. The [(LCu)2H]+ cation also inserts phenylacetylene to afford a gem-dicopper vinyl cation, a rare example of the insertion of carbon-carbon multiple bonds into a copper hydride.
The second part of this thesis describes the synthesis and structural characterization of the first boryl-bridged dicopper cation {[(SIDipp)Cu]2(μ-B(O2C6H4)}+ BF4–. The solid state structure shows a bent arrangement about the boryl with a short intermetallic distance of 2.4082(2) Å. The boryl-bridged dicopper cation deprotonates phenylacetylene to form a phenylacetylide dicopper complex. It also readily reacts with methanol to form the hydride-bridged dicopper cation. Density functional theory (DFT) calculations were applied to give further insight into the nature of the metal–boron bonds in comparison to the mononuclear analogue. The two electrons contributed by the bridging boryl are shared between the boron and the two copper centers in the [(LCu)2B]+ core. This three-center, two-electron bonding orbital is lower-lying in energy in comparison to the Cu−B σ-bonding molecular orbital in the mononuclear analogue, consistent with a less nucleophilic Cu–B bond.
The NHC ligand also stabilizes an isoleptic series of dinuclear μ-fluoro cations of copper(I), silver(I), and gold(I). In these complexes, a single fluoride acts as the sole bridging ligand between the two group 11 metal centers of the form [(LM)2(μ-F)]+. All three cations are highly sensitive to adventitious moisture, readily forming the hydroxide-bridged dinuclear cations. The gold(I) complex is the most reactive. It activates the C-Cl bonds of CD2Cl2 and adds rapidly across an allene C=C bond to form an allylic C–F bond, and a vinyl anion bound asymmetrically to the two gold(I) centers.
| Identifer | oai:union.ndltd.org:GATECH/oai:smartech.gatech.edu:1853/54331 |
| Date | 07 January 2016 |
| Creators | Wyss, Chelsea Marie |
| Contributors | Sadighi, Joseph P., Wilkinson, Angus P. |
| Publisher | Georgia Institute of Technology |
| Source Sets | Georgia Tech Electronic Thesis and Dissertation Archive |
| Language | en_US |
| Detected Language | English |
| Type | Dissertation |
| Format | application/pdf |
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