More

Abstract: Developing methodologies to synthesize high-value products efficiently from simple substrates with control over the reactivity and selectivity is highly favored by the chemical industry. Employing assisted tandem catalysis, where serial reactions can be carried out in one pot, to achieve streamlined complex syntheses significantly reduces the number of steps and waste. Harnessing spatial and temporal control in catalysis enables approaches toward one-pot transformations and allows the integration of several catalytic processes. Ferrocene-based ligand_x005f_x0002_supported metal complexes represent a promising class of catalysts that can incorporate redox control over catalytic processes. We have developed a redox-controlled selective hydroamination reaction catalyzed by (thiolfan*)Zr(NEt2)2 (thiolfan*= 1, 1'-bis (2,4-di-tert-butyl-6-thiophenoxy)ferrocene). In situ switching of the catalyst’s state during the reaction enables selectivity toward different substrates (Chapter 2). Incorporating the greenhouse gas CO2 into N-carboxyanhydrides (NCAs) followed by subsequent NCA utilization illustrates the possibility of integrating two synthetic steps in one vessel to afford a valuable material with possible CO2 recycling. To demonstrate the immense potential of integrating multi-step transformations in one pot, we developed a set of sustainable conditions for NCA synthesis (Chapter 3). Moreover, several metal catalysts supported by ferrocene-based ligands were found to catalyze NCA polymerization in the presence of a co_x005f_x0002_catalyst. To establish an integrated system composed of two incompatible processes, we aimed to compartmentalize the active reagents for each step. The structure of the ferrocene-based pro-ligand was modified for surface anchoring. Our efforts toward immobilizing ferrocene-supported metal catalysts onto conductive surfaces pave the way of achieving spatiotemporal control over the processes of NCA synthesis and polymerization (Chapter 4). In addition to the redox-switchable characteristic, ferrocene-based compounds provide a unique platform to support lanthanides and engender distinctive optical properties to them. We synthesized and characterized a series of ytterbium complexes displaying an ultra-narrow absorption in the ultraviolet-visible (UV-Vis) region. The extraordinarily narrow linewidth observed for (thiolfan)YbCl(THF) (thiolfan = 1,1′-bis(2,4-di-tert-butyl-6-thiomethylenephenoxy)ferrocene) allows us to investigate its applications toward magnetic field and liquid cell quantum sensing (Chapter 5)