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N,N’-Dimethyimidazolium-2-Carboxylate as a Ligand Precursor for the Accession of a Constrained Olefin Dimerization Catalyst

Date: 2020-01-01

Creator: Michael Harris

Access: Open access

A significant market share of modern plastics is held by long-chain hydrocarbon polymers, such as polyethylene and polypropylene, properties of which can be dramatically changed by addition of linear α-olefins. Production of linear α-olefins involves the creation of many unwanted byproducts, representing significant quantities of both economic and ecological waste. While catalysts have been designed to selectively produce industrially useful olefins, these catalysts often encounter challenges such as synthesis of other unwanted byproducts, slow reaction times, and difficulty of synthesis. Based on one such prior catalyst, we report here synthetic work towards a cobalt catalyst with a constrained N-heterocyclic carbene supporting ligand predicted to allow for more favorable product distributions. Synthesis of two precursors to a sterically unhindered N-heterocyclic carbene, as well as development of a synthetic protocol for the coordination of N,N’- dimethylimidazolium-2-carboxylate to Cp*Co(ethene)2 was completed. Activation of the precatalyst and preliminary catalytic experiments were performed, though abbreviated research periods made complete analysis impossible. Finally, we report evidence of the formation of a novel cobalt-NHC dimer as a temperature controlled byproduct of the desired catalyst synthesis.

Activation of Hydrogen by Sterically Modulated Coinage Metal Catalysts via Mutual Quenching of Hard/Soft Acid/Base Mismatches

Date: 2024-01-01

Creator: Zach Leibowitz

Access: Open access

To mitigate the devastating environmental impacts of climate change in the coming decades, it is imperative that we replace the use of fossil fuels with renewable energy sources such as wind, solar, and hydroelectric. As these renewable energy sources are inherently intermittent, there exists a need for sustainable mechanisms to store renewable energy for later use. While the direct use of dihydrogen (H2) as a combustible fuel would allow for energy storage without the harmful release of carbon dioxide (CO2) upon combustion, the practicality of H2 as a synthetic fuel is limited by its low volumetric energy density. Combining sustainable H2 production (e.g. electrolysis using energy from renewable sources) with subsequent carbon fixation (e.g. the hydrogenation of CO2) represents a promising pathway to the sustainable production of high-density synthetic fuels. We hypothesize that such a process could be catalyzed by an IPr**-supported catalyst containing a hard/soft acid/base (HSAB) mismatch, with a polarizable coinage metal acting as a soft acid. As such, the aim of our project is the construction of a catalogue of IPr**-supported copper, silver, and gold catalysts that we anticipate will facilitate the heterolysis of dihydrogen and subsequent hydrogenation of CO2. In the present paper, we report the synthesis and characterization of an IPr**-silver complex which will serve as a precursor to many of our proposed HSAB mismatch catalysts and discuss next steps as we construct our catalogue of catalysts.