Bisphosphine ligands, metallamacrocycles and a solid-supported alkene metathesis catalyst

Nichols, David Andrew (2003) Bisphosphine ligands, metallamacrocycles and a solid-supported alkene metathesis catalyst. PhD thesis, University of Glasgow.

Abstract

The aim of this work was to develop a solid-supported alkene metathesis catalyst. The initial strategy involved two new bisphosphine ligands, DPEN I and DPPN II, and the short and efficient syntheses of these ligands from 2,7-dihydroxynaphthalene are described. The platinum, palladium and ruthenium complexes of ligands I and II were investigated. The ligands were found to favour bridging metal centres to form dimeric or oligomeric complexes. The isolation and structures of three metallamacrocycles formed with platinum(II) are discussed. It was found that the thermodynamically favoured structures were the cis, cis-dimers and that isomerisation to these was catalysed by excess ligand. The bisphosphine ligands were not suitable for use in a solid-supported metathesis N-heterocyclic carbene ligand. The synthesis of bis-mesityl diamine III from L-tyrosine methyl ester is described. Diamine III was immobilised on polystyrene resin and then converted to metathesis catalyst IV. The extensive optimisation carried out in the solid phase synthesis of IV is discussed. A number of diene substrates were synthesised and the supported catalyst was tested for ring closing metathesis activity with good results. However, no enantioselectivity was observed when using the catalyst for RCM of prochiral trienes.

• Item Type: Thesis (PhD)
• Qualification Level: Doctoral
• Keywords: Metathesis (chemistry), ligands (biochemistry), transition metal catalysts.
• Subjects: Q Science > QD Chemistry; Q Science > QH Natural history > QH345 Biochemistry
• Colleges/Schools: College of Science and Engineering > School of Chemistry
• Supervisor's Name: Armstrong, Dr. Susan K. and Cross, Dr. Ron
• Date of Award: 2003
• Depositing User: Enlighten Team
• Unique ID: glathesis:2003-84548
• Copyright: Copyright of this thesis is held by the author.
• Date Deposited: 23 Aug 2024 11:42
• Last Modified: 23 Aug 2024 13:26
• Thesis DOI: 10.5525/gla.thesis.84548
• URI: https://theses.gla.ac.uk/id/eprint/84548