|Ph.D Student||Slutsky Smith Elana|
|Subject||Novel Triazole-Based Ligands and Metal Complexes: Syntheses,|
Properties, and Reactivities
|Department||Department of Chemistry||Supervisor||Professor Mark Gandelman|
|Full Thesis text|
Catalyst discovery requires either accurate prediction of the best catalyst for a given process prior to synthesis or efficient synthesis of a wide variety of potential catalysts, followed by screening for catalytic activity. Since such predictions are extremely difficult, a combinatorial approach to tailor-made, fine-tuneable ligands for organometallic catalysts is desired. In order to obtain robust systems, covalent assembly was required. Furthermore, bidentate systems were desired due to the greater stability and rigidity they confer to their organometallic complexes, as compared to monodentate analogs. Thus a combinatorial approach to bisphosphine ligands based on a triazole core was developed. This method utilized the selective triazole forming reaction of phosphorus donor-containing azide and alkyne monomers. These protected phosphine-containing monomers were each synthesized in two steps from commercial starting materials. Although the expected cycloaddition product was the 1,5-substituted regioisomer, a rearrangement of triazole substituents led to the formation of 4,5 substituted triazoles as the main product. Following deprotection, these novel products were selectively coordinated to transition metal precursors. In addition, it was shown that the triazole backbone of these ligands is highly modifiable and can be either alkylated or deprotonated to form a triazolate based salt. Moreover, with certain metal precursors, the coordination mode depends on the charge of the triazole backbone. Initial results in the field of coordination polymer synthesis were obtained.