title: Ring opening metathesis polymerization-derived block copolymers bearing chelating ligands: synthesis, metal immobilization and use in hydroformylation under micellar conditions.
abstract: Norborn-5-ene-(N,N-dipyrid-2-yl)carbamide (M1) was copolymerized with exo,exo-[2-(3-ethoxycarbonyl-7-oxabicyclo[2.2.1]hept-5-en-2-carbonyloxy)ethyl]trimethylammonium iodide (M2) using the Schrock catalyst Mo(N-2,6-Me₂-C₆H₃)(CHCMe₂Ph)(OCMe(CF₃)₂)₂[Mo] to yield poly(M1-b-M2). In water, poly(M1-b-M2) forms micelles with a critical micelle-forming concentration (cmc) of 2.8 x 10⁻⁶ mol L⁻¹; Reaction of poly(M1-b-M2) with [Rh(COD)Cl]₂ (COD = cycloocta-1,5-diene) yields the Rh(I)-loaded block copolymer poly(M1-b-M2)-Rh containing 18 mg of Rh(I)/g of block copolymer with a cmc of 2.2 x 10⁻⁶ mol L⁻¹. The Rh-loaded polymer was used for the hydroformylation of 1-octene under micellar conditions. The data obtained were compared to those obtained with a monomeric analogue, i.e. CH₃CON(Py)₂RhCl(COD) (C1, Py = 2-pyridyl). Using the polymer-supported catalyst under micellar conditions, a significant increase in selectivity, i.e. an increase in the n:iso ratio was accomplished, which could be further enhanced by the addition of excess ligand, e.g., triphenylphosphite. Special features of the micellar catalytic set up are discussed.
authors.affiliation: Lehrstuhl für Makromolekulare Stoffe und Faserchemie, Institut für Polymerchemie, Universität Stuttgart, Pfaffenwaldring 55, D-70550 Stuttgart, Germany.
authors.forename: Gajanan M
authors.initials: GM
authors.lastname: Pawar
authors.forename: Jochen
authors.initials: J
authors.lastname: Weckesser
authors.forename: Siegfried
authors.initials: S
authors.lastname: Blechert
authors.forename: Michael R
authors.initials: MR
authors.lastname: Buchmeiser