Identificador: TDX:867
Autores: García Suárez, Eduardo José
Resumen:
The interest in the palladium(II)-catalysed copolymerisation reaction of carbon monoxide and ethene as well as other reactions involving the formation of the C-C bond is increasing because of the possibilities of application in synthesis of new products and materials. This interest is reflected in the large number of reports published in recent years.Since catalyst degradation to inactive species, is the major cause of the low productivity, considerable research effort is being made to design diphosphine ligands that can prevent them from degrading. Many papers have shown that the introduction of an o-methoxy substituent on the P-aryl rings of the diphosphine enhances the productivity in comparison with the unsubstituted ligands. It has been suggested that both steric and electronic factors are responsible for the positive effect of the o-methoxy groups on catalyst activity.This thesis focuses on elucidating the effect of the o-methoxy group introduced on the P-aryl rings of the diphosphine ligands in the copolymerization reaction of carbon monoxide and ethene from a catalytic and a mechanistic point of view.In the second part, the thesis focuses on the synthesis of new phosphine sulfonated ligands for the less well known reaction of non-alternating copolymerisation of CO and ethene and the applications of the later ligands in the Suzuki-Miyaura cross-coupling reaction in aqueous media.To achieve these objectives, new ligands and neutral, cationic as well as anionic palladium complexes have been synthesised. New alternative synthetic protocols have been developed to: 1) introduce the -OMe group on the P-aryl rings of known and new diphosphine ligands, 2) synthesise new phosphine sulfonated ligands.Catalytic reactions are carried out in different media as well as high pressure NMR experiments in an attempt to better understand the beneficial effect of omethoxy groups and the less well known mechanism of the non-alternating copolymerisation of CO and ethene.Chapter 1 covers the basic literature and most recent development in the alternating copolymerisation of carbon monoxide and ethene, non-alternating copolymerisation of carbon monoxide and ethene and Suzuki-Miyaura crosscoupling >reaction.Chapter 2 discusses the effect of the o-methoxy group on the alternating copolymerisation reaction of carbon monoxide and ethene. Diphosphine ligands 1,2-bis(di(2-methoxyphenyl)phosphino)ethane,1,3-bis(di(2-methoxyphenyl)phosphino)propane are synthesised by an alternative synthetic protocol. Both ligands and their phenyl counterparts for comparative purpose, are used to synthesise neutral and cationic palladium(II) complexes. The complexes are used to catalyse the CO-ethene copolymerisation reaction in either protic or aprotic solvents. In situ and operando high-pressure NMR experiments provide valuable information on catalysis resting states and intermediates. In addition, important steps in the CO/ethene copolymerisation reaction are studied by in situ high-pressure NMR spectroscopy, which helps rationalise the effect of the o-methoxy group.In Chapter 3, the new diphosphine (o-MeO-bdpp) rac-2,4-bis(di(2-methoxyphenyl)phosphino)pentane is synthesised. This ligand is used to synthesise new neutral palladium(II) complexes. The ligand and complexes are fully characterised in solution by multinuclear NMR spectroscopy. This C2-bridged ligand is compared with the C3-bridged ligand and the more rigid ligand bis-cationic diphosphonium-diphosphine 6,7-di(di-2-methoxyphenyl)phosphinyl-2,2,4,4-tetra(di-2-methoxyphenyl)-2l4,4l4-diphosphoniumbicyclo[3.1.1]heptanebis(PF6) (o-MeO-PCP)(PF6)2) in the copolymerisation of CO with ethene in different reaction media in order to compare the effect of backbone rigidity.Chaper 4 deals with the synthesis of new phosphine sulfonated ligands. The ligands are prepared through a new and sustainable synthetic route and used to synthesise new palladium(II) anionic complexes. The later anionic complexes are used in the less well known non-alternating copolymerisation reaction of carbon monoxide and ethene and compared with other phosphine sulfonate ligands that have been applied in this kind of catalysis. In addition, high pressure NMR experiments are carried out in order to go further into the mechanism of this polymerisation reaction.Furthermore, taking advantage of the fact that the new phosphine sulfonated ligands are both water-soluble and air stable, they are successfully applied in palladium-catalysed Suzuki-Miyaura cross-coupling reactions in neat water in conjunction with microwave heating.
Repositori URV