Supported catalysts, from polymers to gold nanoparticles supports

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Sommer, William J.
Weck, Marcus
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In today s world, the need to limit the use of nonrenewable resources and the importance of recycling has been recognized. One important contribution of chemists toward the general goal of limiting their use is to find catalysts that can be reused and recycled thereby limiting the need for expensive metal precursors and metal waste. Strategies to recycle catalysts are multifold and range from the employment of soluble polymers as catalyst supports to the use of membrane-encapsulated catalyst. The use of soluble polymers as a support not only offers the advantage of being soluble under the catalytic reaction conditions but also, to be removable by changing the conditions of the surrounding media. Despite the great potential of these soluble supported catalysts, their use is very limited in today s synthesis. In addition, no set of rules have been established to guide the synthesis of efficient supported catalysts. In order to establish a tool box for the synthesis of supported catalysts, the study of several parameters such as the choice of the support and the choice and the stability of the catalyst are necessary. To establish this set of rules, a limited number of catalytic transformations, were studied. These catalytic reactions are the Heck-Mizoroki, Suzuki-Miyaura and Sonogashira coupling reactions. These transformations became fundamental for the synthesis of drugs and materials. The first and second chapters provide background information by describing and evaluating the main supports that were previously used for catalysts and the two main catalysts that are used in this thesis, the palladium pincer complex and the palladium N-heterocyclic complex. In chapter 3, the synthesis of a soluble polymer supported catalyst is described. The polymer chosen for the study is poly(norbornene), and the catalyst is a 1,3-disubstituted benzene ligand with sulfurs in the side-chains able to chelate to the metal center, better known as pincer ligand. These ligands are abbreviated by the three atoms that coordinate to the metal center, in this study, SCS. The metal used for the investigation of the activity of this supported pincer is palladium. The importance of the nature of the linkage on the stability of the Pd-SCS pincer complex has been reported in the literature, leading to the synthesis of Pd-SCS pincer complex tethered to the polymer via an ether and an amide linkage. The synthesized poly(norbornene) supported Pd-SCS pincer complexes were evaluated using the Heck transformation of iodobenzene with n-butyl acrylate. Kinetic studies and leaching tests using poly(vinyl pyridine) and mercury were carried out resulting in the conclusion that the active species during the catalysis is not the palladium pincer complex but a leached palladium (0) species. In chapter 4, Pd-PCP pincer complexes with the ether and amide tether were synthesized. Kinetic and poisoning studies were carried out resulting in a similar conclusion. Furthermore, 31P NMR experiments were conducted to investigate the unstability of the complex. Following this study, in-situ XAS as well as computational calculations were carried out. The conclusion from this sinvestigation argues that triethylamine is a key ingredient for the decomposition of the Pd-PCP complex. The overall conclusion from these two different studies is thta Pd(II) pincer complexes decomposes during the Heck reaction when triethylamine is used for the coupling of iodobenzene to n-butyl acrylate in DMF at 120 ºC. Stemming from this investigation, a reported more stable complex, Pd-NHC, was tethered onto poly(norbornene). The system was evaluated using Suzuki-Miyaura, Heck and Sonogashira reactions. Similar poisoning and kinetic studies were utilized to investigate the stability of the supported NHC Pd complexes. The result of this investigation suggests that supported Pd-NHC complexes are stable under Suzuki-Miyaura and Sonogashira but decompose under Heck conditions. However, when the system was recycled, a decrease in activity for the Suzuki-Miyaura transformation and solubility was observed. In chapter 6, gold monolayer protected clusters (MPC) were investigated as potential candidates as supports. To examine the potential of MPC as a support, a NHC-Pd complex was graphted onto the particles. To functionalize the gold nanoparticles, a new method was developed. Using azide moieties added to the gold nanoparticles, the catalyst was added via microwave assisted 1,3 dipolar cycloaddition. The system was evaluated using Suzuki-Miyaura transformations under microwave conditions. The system exhibited quantitative conversions for a variety of substrates. However, when the system was recycled, aggregation of the particles and decrease in catalytic activity was observed. In summary, this thesis describes the synthesis and evaluation of poly(norbornene) supported Pd-pincer and Pd-NHC complexes and of gold nanoparticles supported Pd-NHC complex. It also detail the combination of kinetic and poisoning studies developed to evaluate a potential supported catalyst.
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