Also, an improved, high-yield synthesis of Ru-1 has been presented. Unless noted otherwise, all manipulations were performed in a Labmaster glovebox MBraun; Garching, Germany or by standard Schlenk techniques under N2 atmosphere.
Received Jan 11; Accepted Mar The license is subject to the Beilstein Journal of Organic Chemistry terms and conditions: Summary Norbornene- N,N-dipyridyl carbamide M1 was copolymerized with exo,exo-[2- 3-ethoxycarbonyloxabicyclo[2.
In water, poly M1-b-M2 forms micelles with a critical micelle-forming concentration cmc of 2. The Rh-loaded polymer was used for the hydroformylation of Buchmeiser metathesis polymerization under micellar conditions.
The data obtained were compared to those obtained with a monomeric analogue, i. Using the polymer-supported catalyst under micellar conditions, a significant increase in selectivity, i.
Special features of the micellar catalytic set up are discussed. In cases where reactions are run in polar media, the catalyst is best located inside the hydrophobic micellar core, where, upon micelle formation of the functionalized block copolymer, the monomer will also accumulate.
This leads to high educt concentrations at the polymer-bound catalyst, often resulting in high reaction rates in water [ 8 ]. We recently reported on the synthesis of RhI and IrI complexes of N,N-dipyridylacetamide and their use in hydroformylation reactions [ 9 ].
Here, we report on the immobilization of a Rh-N,N-dipyridylacetamide-based catalyst on a soluble, amphiphilic, ring-opening metathesis polymerization- ROMP derived block copolymer and its use in hydroformylation [ 10 ] under micellar conditions [ 3511 ].
This medium activity and selectivity dipyridylamide-based Rh I -catalyst was chosen in order to identify the potential advantages of a micellar setup.
Results and Discussion Synthesis of monomers The synthesis of norbornene- N,N-dipyridyl carbamide M1 was accomplished via reaction of norborneneylcarboxylic acid chloride with dipyridylamine in the presence of triethylamine as described elsewhere [ 9 ].
It entailed the reaction of 7-oxanorbornene-2,3-dicarboxylic anhydride with 2- N,N-dimethylamino ethanol, conversion of the free carboxylic acid 1 into the corresponding acid chloride with SOCl2 and reaction of the acid chloride with dry ethanol to form the diester 2.
Finally, compound 2 was converted into M2 via quaternization of the tertiary amine with methyl iodide.Pulsed-Addition Ring-Opening Metathesis Polymerization: Catalyst-Economical Syntheses of Homopolymers and Block Copolymers John B.
Matson, Scott C. Virgil, and Robert H. Grubbs* Center for Catalysis and Chemical Synthesis, DiVision of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California Olefin Metathesis by Group VI (Mo, W) Metal Compounds. By Frédéric Lefebvre, Yassine Bouhoute, Kai C.
Szeto, Nicolas Merle, Aimery de Mallmann, Régis Gauvin and Mostafa Taoufik (iv) ring-opening metathesis polymerization, (v) acyclic diene metathesis, and (vi) ethenolysis. Buchmeiser et al.
have increased the catalytic activity of. REACTION MECHANISM OF OLEFIN METATHESIS WITH A NOVEL MOLYBDENUM CATALYST used for polymerization of olefins but these catalysts are very sensitive to functional groups at the monomers.
M. R. Buchmeiser, S.
Sen, J. Unold, W. Fey, Angew. Chem Int. Ed. , 53, 2) Manuscript in preparation. A highly electrophilic dicationic ruthenium-alkylidene complex is used in ring-opening metathesis polymerization and in cyclopolymerization.
A highly electrophilic dicationic ruthenium-alkylidene complex is used in ring-opening metathesis polymerization and in cyclopolymerization. As shown by Michael R. Buchmeiser and co-workers at the. Contributions of Olefin Metathesis to Material Science. Michael R.
Buchmeiser, University of Stuttgart, Germany. This presentation will address the impact of metathesis-based polymerization techniques such as ring-opening metathesis polymerization (ROMP), 1-alkyne polymerization and the cyclopolymerization of diynes on polymer-based material science.
Ring opening metathesis polymerization (ROMP) is a versatile tool for preparing side chain liquid crystalline polymers (SCLCPs) with different mesogenic units.
Riegler S., Fuchs G., Slugovc C., Stelzer F.
Liquid Crystalline Polymers by Metathesis Polymerization. In: Buchmeiser M.R. (eds) Metathesis Polymerization. Advances in Polymer.