Showing 1 - 8 of 8 Items
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.
Investigating the Effect of Side Chains with Hydrogen Bonding Capabilities on Peptoid Catalysts for Enantioselective Trifluoromethylation of 4-Chlorobenzaldehyde Access to this record is restricted to members of the Bowdoin community. Log in here to view.
- Restriction End Date: 2025-06-01
Date: 2020-01-01
Creator: Rebecca Londoner
Access: Access restricted to the Bowdoin Community
Determination of the Relationship Between Peptoid Catalyst Oligomeric Length and Catalytic Enantioselectivity of Trifluoromethylation of Aldehydes Access to this record is restricted to members of the Bowdoin community. Log in here to view.
- Restriction End Date: 2025-06-01
Date: 2020-01-01
Creator: Katharine Toll
Access: Access restricted to the Bowdoin Community
Reactions Responsible for Aging in Wood-Based Pyrolysis Oil: Synthesis and Characterization of a Coniferyl Alcohol Dimer
Date: 2021-01-01
Creator: Alejandro Garcia
Access: Open access
- The negative environmental impact and the diminishing supply of fossil fuels demand a renewable alternative. Pyrolysis oils produced from the decomposition of biomass, like wood, are a potential fuel substitute for energy production and a feedstock alternative for manufacturing value-added chemicals. The possibilities offered by pyrolysis oils are offset by oil instability. The oils contain reactive compounds, such as small aldehydes, conjugated aromatics, and acids that over time react and produce higher molecular mass products. This instability manifests as an increase in viscosity by a process referred to as aging. One chemical component, coniferyl alcohol, is proposed to react with formaldehyde under the acidic oil conditions to produce a dimer. In our lab, researchers have detected the coniferyl alcohol dimer in authentic oil samples and have simulated the reaction under conditions that removes the complexity of the pyrolysis oil matrix. This study focused on the synthesis, isolation, and characterization of the dimer structure by employing NMR analysis. GC/MS analysis of a successful synthesis of the dimer showed multiple dimers were produced, but there was one principal product. The NMR analysis of this dimer was used to elucidate the geometry, providing evidence that the product has E stereochemistry for the double bond and trans stereochemistry in the acetal ring. Confirmation of the principal structure provides support for the dimerization mechanism and will allow for future research to address instability of pyrolysis oils.
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.
Benchmarking Ab Initio Computational Methods for the Quantitative Prediction of Sunlight-Driven Pollutant Degradation in Aquatic Environments
Date: 2016-05-01
Creator: Kasidet Trerayapiwat
Access: Open access
- Understanding the changes in molecular electronic structure following the absorption of light is a fundamental challenge for the goal of predicting photochemical rates and mechanisms. Proposed here is a systematic benchmarking method to evaluate accuracy of a model to quantitatively predict photo-degradation of small organic molecules in aquatic environments. An overview of underlying com- putational theories relevant to understanding sunlight-driven electronic processes in organic pollutants is presented. To evaluate the optimum size of solvent sphere, molecular Dynamics and Time Dependent Density Functional Theory (MD-TD-DFT) calculations of an aniline molecule in di↵erent numbers of water molecules using CAM-B3LYP functional yielded excited state energy and oscillator strength values, which were compared with data from experimental absorption spectra. For the first time, a statistical method of comparing experimental and theoretical data is proposed. Underlying Gaussian functions of absorption spectra were deconvoluted and integrated to calculate experimental oscillator strengths. A Matlab code written by Soren Eustis was utilized to decluster MD-TD-DFT results. The model with 256 water molecules was decided to give the most accurate results with optimized com- putational cost and accuracy. MD-TD-DFT calculations were then performed on aniline, 3-F-aniline, 4-F-aniline, 3-Cl-aniline, 4-MeOacetophenone, and (1,3)-dimethoxybenzophenone with CAM-B3LYP, PBE0, M06-2X, LCBLYP, and BP86 functionals. BP86 functional was determined to be the best functional. Github repository: https://github.com/eustislab/MD_Scripts
Phenylisonitrile Ligand Synthesis and Coordination to Cobalt to Form a Catalyst for the Selective Dimerization of Linear Alpha Olefins Access to this record is restricted to members of the Bowdoin community. Log in here to view.
- Restriction End Date: 2026-06-01
Date: 2023-01-01
Creator: Colleen Hughes McAloon
Access: Access restricted to the Bowdoin Community
Synthesis and Metalation of a Bifunctional Ligand for Hydrogen Activation This record is embargoed.
- Embargo End Date: 2028-05-18
Date: 2023-01-01
Creator: Eliana Roberts
Access: Embargoed