Catalyst-Controlled Divergent C–H Functionalization of Unsymmetrical 2-Aryl Cyclic 1,3-Dicarbonyl Compounds with Alkynes and Alkenes A problem faced within the area of C–H functionalization is achieving siteselectivity when several similar C–H bonds are present within a given compound. One solution to this problem is the development of reactions that employ different catalytic systems to control the required selectivity. Herein, it is shown that such catalyst-controlled selectivity could be achieved on 2-aryl cyclic 1,3-dicarbonyl compounds where there exist two potential, non-adjacent sites for C–H functionalization. Examples demonstrate the palladium- and ruthenium-catalysed oxidative annulations of the 2-aryl cyclic 1,3-dicarbonyl substrates with alkynes, as well as with alkenes, where initial C–H bond cleavage occurs at one of two potential sites, depending on the catalyst used, which give unique products. 1,4-Rhodium(III) Migration in the One-Carbon Oxidative Annulations of 2-Arylphenols, Benzamides, and Benzoic Acids with 1,3-Enynes Oxidative annulations of 2-arylphenols, benzamides, and benzoic acids with alkynes and enynes are precedented and provide a range of heterocyclic products. However, in these examples, either the alkyne or enyne acts as a two-carbon annulation partner, reacting only across the alkynyl moiety. Herein, a more expansive scope of a previously published process in which 1,3-enynes, possessing allylic hydrogen atoms cis to the alkyne, undergo oxidative annulations with the three aforementioned classes of substrates as a one-carbon annulation partner is described. Proposed to occur via the 1,4-migration of a rhodium(III) species, annulated products were formed from a range of 1,3-enynes and substrates possessing a variety of functional groups.

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This dissertation describes the synthesis, antimicrobial properties, and catalytic activity of a variety of eta5-ligand rhodium and iridium complexes. Cp*RM(beta-diketonato)Cl (Cp*R = R-substituted tetramethylcyclopentadienyl ligand) complexes were found to have selective activity against Mycobacterium smegmatis, with activity highly dependent upon the substituents on the Cp*R ligand as well as on the beta-diketonato ligand. These complexes were synthesized in good yield from the reaction of the chloro bridged dimers ([Cp*RMCl2]2) with the desired beta-diketonato ligand under basic conditions. All complexes were fully characterized by 1H and 13C NMR. Twenty single crystal X-ray structures were solved. The success of these syntheses led to investigation of another beta-diketonato ligand: 1,1,1,5,5,5-hexafluoroacetylacetonate (hfac). Though many metal complexes of this ligand are known, reaction with [Cp*MCl2]2 did not yield the desired Cp*M(hfac)Cl complexes. Instead, a variety of products were obtained, three of which were characterized crystallographically. The most interesting structure featured a non-coordinating trifluoroacetate (TFA) anion and a [Cp*Ir]3Na1O4 cubane structure, which is an unprecedented and highly unusual arrangement for iridium. Attempts to synthesize this cluster rationally through reactions of [Cp*IrCl2]2 with TFA yielded instead a chloro bridged [Cp*IrCl(TFA)] dimer. Reaction of [Cp*MCl2]2 with 1,1,1-trifluoroacetylacetonate (tfac) yielded the expected Cp*M(tfac)Cl complex, indicating that the problem lies with using hfac as a ligand for Cp*M(III) complexes. Finally, the indenyl effect was investigated for the oxidative annulation of 2-phenylimidazole with 1-phenyl-1-propyne catalyzed by a series of methyl-substituted [(indenyl)RhCl2] dimers. [(Ind*)RhCl2]2 was found to have significantly greater activity than [Cp*RhCl2]2 (100% vs. 51%). Two plausible catalytic cycles were proposed, one of which invokes a ring slip transition state. Though it is unclear if the "indenyl effect" is responsible for this differing activity, it is certainly apparent that using an indenyl ligand has a notable effect in this catalytic reaction. Cyclometalation was also investigated stoichiometrically for 2-phenyl-1H-imidazole and 1-phenylpyrazole and found to proceed readily for [(Ind*)RhCl2]2. Additionally, the crystallographic structure of a Rh+ /Rh– ionic pair was solved. Ionic pairs such as this are rarely found in the literature. / Doctor of Philosophy / This dissertation deals with the uses of a series of unusual compounds containing the metals rhodium and iridium. Though these are rare and expensive metals, the uses and benefits described in this dissertation far outweigh the costs. Overall, the compounds described in this dissertation are colorfully characterized as “piano stool” compounds because of their overall shape and appearance. The metal, either rhodium or iridium, occupies a central point in the complex. On top of the metal is a “flat” organic group that gives the appearance of the seat of the piano stool. Below the metal, there are three other groups that look like the legs of the piano stool. By appropriate choice of the metals and the surrounding groups, special properties can be designed into these “piano stool” complexes. Chapter 2 describes the synthesis of a series of complexes where the “flat” group is a variant of a five-membered carbon ring compound known as cyclopentadienyl, the metal is rhodium or iridium, and two of the three legs come from a family of compounds known as acetylacetonates (acac). This series of piano stool compounds display antimicrobial activity against a class of pathogens known as mycobacteria, an example of which causes the disease tuberculosis. Changing the cyclopentadienyl group and the acac group allows for this antimicrobial activity to be tuned. In the following chapter, attempts to make the same type of compound described in the paragraph above with fluorine-substituted acacs gave some very unexpected results. The most surprising result was a very unusual cube-shaped structure containing 3 iridium atoms, 1 sodium atom, and 4 oxygen atoms, which is an unprecedented arrangement for iridium. Finally, there is a specific example of a flat group for the piano stool known as indenyl. Indenyl is intriguing because it can change shape from a flat group to a bent group. In doing this, it provides more space around the metal for other molecules to bind. The result of this work shows that piano stool compounds created with this indenyl group are more active and selective for carrying out a catalytic reaction to make new ring systems that could have potential use in the synthesis of new flavorings, fragrances, and even pharmaceuticals.