Towards Nickel Boride Catalyzed C-C Coupling Reactions

• Main Author: Lakó, Ágnes
• Format: Others
• Language: English
• Published: KTH, Skolan för kemivetenskap (CHE) 2017
• Subjects: heterogeneous catalysis; nickel catalysis; coupling reactions; cross-coupling; homocoupling; Engineering and Technology; Teknik och teknologier
• Online Access: http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-216398

This thesis focuses on the study of nickel boride as a catalyst in various coupling reactions. The nickel boride catalyst was investigated in three different coupling reactions, the experiments aimed at understanding the activity and catalytic properties of nickel boride. We successfully synthetized the nickel boride catalyst, alongside with the cobalt and iron boride. Different methods of preparation were compared and we concluded, that the differences in the preparation, such as solvent and atmosphere, influence the activity of the catalyst in coupling reactions. We found that the most suitable solvent for preparing nickel boride is anhydrous methanol, thus we proceeded our research with this catalyst. In the case of the Sonogashira cross-coupling we found that the homocoupling of the acetylene starting material is a side reaction we could not exclude. However, with the proper solvent it is possible to shift the reaction towards homocoupling, without the formation of the heterocoupling product. Thus, we decided to investigate the Glaser homocoupling between acetylenes. In the case of the Sonogashira coupling only TLC was used to examine the reaction mixture. However, in the case of Glaser coupling, after pre-investigations we developed a gas chromatography method for analyzing the reaction mixtures. We learned, that the homocoupling only results in trace amounts (2-4%) of product. Previous investigations in our research group showed, that the nickel boride could catalyze Suzuki-Miyaura-type couplings. Examining this reaction all three metal borides were tested; however, the reactions only led to the desired product with nickel boride. Analyzing the reaction with gas chromatography we learned that the choice of solvent influences the stability of the starting materials and the formation of side products. Reactions with different starting materials, in different solvents, with different bases were analyzed. The effect of microwave irradiation was also examined. Based on the results we concluded, that with nickel boride it is not possible to achieve high yields in coupling reactions.