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Polymer Bound Water-Soluble Metal Phosphine Complexes-Preparation, Characterisation and Catalytic Application

Malmström, Torsten LU (1998)
Abstract (Swedish)
Popular Abstract in Swedish

En ny typ av vattenlösliga fosfin ligander har utvecklats. Dessa fosfiner har använts som ligander i rhodium katalyserade tvåfasreaktioner.Komplexbildningen mellan de nya liganderna och olika metalcentra har studerats och de nya komplexen har använts i hydroformylerings- och hydreringsreaktioner. Polymerbundna kirala fosfiner har använts i enantioselektiv hydrering.
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)... (More)
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. (Less)
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author
opponent
  • Professor Sheldon, R, Delft University of Technology, Julianalaan, 2628 Delft, The Netherlands
organization
publishing date
type
Thesis
publication status
published
subject
keywords
enantioselective, SAP, hydrogenation, hydroformylation, catalysis, biphasic, rhodium, poly-ethylene imine, poly-acrylic acid, polymers, water-soluble, phosphines, Inorganic chemistry, Oorganisk kemi
pages
185 pages
publisher
Torsten Malmström. Inorganic chemistry 1, Chemical Center, Box 124, Lund University, 22100 Lund, Sweden,
defense location
sal D, Chemical Center
defense date
1998-06-05 10:15
external identifiers
  • Other:ISRN: LUN KDL/NKOO--98/1031--SE
language
English
LU publication?
yes
id
ee38d37b-b7cc-446f-9216-dbdb7da3d37c (old id 38781)
date added to LUP
2007-08-01 14:09:31
date last changed
2016-09-19 08:45:13
@misc{ee38d37b-b7cc-446f-9216-dbdb7da3d37c,
  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.},
  author       = {Malmström, Torsten},
  keyword      = {enantioselective,SAP,hydrogenation,hydroformylation,catalysis,biphasic,rhodium,poly-ethylene imine,poly-acrylic acid,polymers,water-soluble,phosphines,Inorganic chemistry,Oorganisk kemi},
  language     = {eng},
  pages        = {185},
  publisher    = {ARRAY(0x98121b8)},
  title        = {Polymer Bound Water-Soluble Metal Phosphine Complexes-Preparation, Characterisation and Catalytic Application},
  year         = {1998},
}