Use this URL to cite or link to this record in EThOS: http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.650631
Title: Towards redox control of organometallic catalysts bearing ferrocene-based ligands
Author: Du, Shuoren
Awarding Body: Imperial College London
Current Institution: Imperial College London
Date of Award: 2013
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Abstract:
This project focuses on the design and synthesis of redox active palladium and rhodium complexes containing ferrocene moieties, and the influence of switching the oxidation state of the ligand on the catalytic behaviour of the metal centre. The redox effect on the catalyst is investigated via carbonylation, hydrogenation and Suzuki cross-coupling reactions. Chapter 1. Introduction to redox-controlled catalysis and palladium-catalyzed carbonylation reactions. The categorization of redox active ligands, and the use of electrochemistry as a tool for choosing the right chemical redox agent are discussed. The aims of the project are outlined. Chapter 2. Chemical oxidation of a series of palladium complexes containing bidentate ferrocen-1,1'-diphosphines, and their catalytic behaviour towards the carbonylation reactions of aryl halides compared with the non-oxidized complexes are reported. A hypothesis is proposed to explain the difference in the catalytic reactivities of the same complex with a different state of charge of the ligand. Chapter 3. The synthesis of a series of new bidentate ligands from ferrocenylamine and their palladium complexes is reported. The electrochemical properties of these palladium N-P complexes are described, as well as their performance as catalysts for carbonylation reactions. Chapter 4. An improved method for the purification of halogenated feorrcenes is included in this chapter. The synthesis of other groups of ferrocene-based ligands and their complexation towards new palladium N-N complexes is reported. Chapter 5. Attempts to realize redox control on other catalytic processes, such as palladium-catalyzed Suzuki cross-coupling reactions and rhodium-catalyzed hydrogenation, is discussed. Chapter 6. Conclusions and future work of this project. Chapter 7. Experimental details. References are included in each of these chapters.
Supervisor: Long, Nicholas Sponsor: China Scholarship Council
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID: uk.bl.ethos.650631  DOI: Not available
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