@phdthesis{ee38d37bb7cc446f9216dbdb7da3d37c,
title = "Polymer Bound Water-Soluble Metal Phosphine Complexes-Preparation, Characterisation and Catalytic Application",
abstract = "Four new water-soluble phosphines have been prepared by utilising water-soluble polymers as charge carrying units. Coupling of methyl-4-(diphenylphosphino)-benzyl-amine or 4-diphenylphosphino benzaldehyde to poly-acrylic acid and poly-ethylene imine, respectively, afford the ligands PAA-PNH and PEI-PNH. Coupling of (2S,4S)-4-diphenylphosphino-2-di-phenylphosphino-methylpyrrolidine (PPM) or (R,R)-3,4-bis(diphenylphosphin)pyrrolidine (pyrphos) to poly-acrylic acid give the ligands PAA-PPM and PAA-pyrphos, respectively. Reaction of PAA-PNH with [Rh(CO)2(acac)] give a complex which is active in the hydroformylation reaction of different olefins, both as a supported aqueous phase catalyst (SAP) and as a catalyst in biphasic (H2O/toluene) hydroformylation reactions. Reaction of PAA-PNH and PEI-PNH with [Rh(NBD)2]OTf give the complexes [Rh(P)2(NBD)]+. Complexes derived from both these ligands are active as catalysts in hydrogenation reactions of both water-soluble and water-insoluble olefins. Reaction of PAA-PPM and PAA-pyrphos with [Rh(NBD)2]OTf give the complexes [Rh(P-P)(NBD)]+ (P-P=PAA-PPM and PAA-pyrphos), which have been applied as catalysts in biphasic enantioselective hydrogenations of different dehydro amino acids. The hydrogenation of a-acetamido cinnamic acid with [Rh(P-P)(NBD)]+ (P-P=PAA-PPM and PAA-pyrphos) give as best N-acetyl phenyl alanine in 89 and 82 % ee, respectively. The enantioselectivity for the PAA-PPM based catalysts are dependent on the phosphorus content of the ligand and the ionic strength of the aqueous solution. [Rh(DPPBTS)(NBD)]OTf (DPPBTS=tetrasulfonated bis(diphenyl phosphino) butane) has been prepared and used to study pH effects on the rate of hydrogenation in water. The hydrogenation of a-acetamido acrylic acid is extremely fast below the pKa of the substrate, while the reaction is dramatically slower at higher pH. This change in rate is due to a changed coordination mode of the substrate at higher pH.",
keywords = "enantioselective, SAP, hydrogenation, hydroformylation, catalysis, biphasic, rhodium, poly-ethylene imine, poly-acrylic acid, polymers, water-soluble, phosphines, Inorganic chemistry, Oorganisk kemi",
author = "Torsten Malmstr{\"o}m",
note = "Defence details Date: 1998-06-05 Time: 10:15 Place: sal D, Chemical Center External reviewer(s) Name: Sheldon, R Title: Professor Affiliation: Delft University of Technology, Julianalaan, 2628 Delft, The Netherlands --- The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Inorganic chemistry (ceased) (LUR000010)",
year = "1998",
language = "English",
publisher = "Torsten Malmstr{\"o}m. Inorganic chemistry 1, Chemical Center, Box 124, Lund University, 22100 Lund, Sweden,",
type = "Doctoral Thesis (compilation)",
school = "Department of Chemistry",
}