Olefin Metathesis and Polymerization Catalysts

Olefin metathesis reaction can be considered as one of the most successful organic reactions with many applications in the low molecular weight range and also in the polymer field. The use of catalysts with their selective and effective transformation properties in olefin metathesis I polymerization systems is a growing interest. There has been great effort and competition in developing active and commercially useful catalysts. The main aim of this ASI was to gather several research groups and also the people from industry. to present existing knowledge and latest results in the field. A wide range of topics through homogeneous and heterogeneous aspects have been considered. Attention has been drawn to the metal-carbene and metallacyclobutane complexes as active species, the initiation mechanisms, the stereochemistry and thermodynamics of these reactions. New catalytic systems for the metathesis of alkenes and alkynes and fot' ring opening polymeriZation I block copolymerization reactions have been introduced. Spectroscopic studies for the characteriZation of catalysts, simulation studies explaining the function of chain carrier species and polymer degradation have also been covered. A detailed industrial report concerning the patents and applications in olefin metathesis I cyc1001efin polymerization area, fabrication and derivation has been presented. This volume contains the main lectures and seminars given at the NATO Advanced Study Institute on " Olefin Metathesis and Polymerization Catalysts: Synthesis, Mechanism and Utilization", held at Akcay. Babkesir. Turkey between 10th and 22nd September 1989.

Inhalt

Overture: Olefin Metathesis and Metathesis Polymerization. A Historical Perspective.- The Stereochemistry of Metathesis of Acyclic and Cyclic Olefins.- Electrochemical Generation of Catalysts for Alkene Metathesis.- Catalysts for the Homogeneous Metathesis of Functionalized Olefins.- Block Copolymers by Anionic to Metathesis Transformation Reactions.- The Kinetics of Polymerization of Cyclopentene.- Tacticity in Polymers Initiated by Metathesis Polymerization: Effect of Catalyst.- Degradation of Polymers by Metathesis Catalysts.- Metathesis Polymerization by Homogeneous Catalysts; Simulations.- General Properties of Supported Metathesis Catalysts.- Surface Functionalization of Supported Catalysts.- Novel Supported Catalysts for Terminal Alkene Metathesis.- Characterisation of Rhenium Oxide/Alumina Metathesis Catalysts.- Stoichiometric Reactions with Reduced Phillips Catalysts.- Catalytic Reactions with Reduced Phillips Catalysts.- Non-Chromium Surface Compounds.- Coordination Chemistry of Silica Supported Cr Ions: Types of Cr(II) Ions on Reduced Samples.- Structural Analysis of Supported Chromium Systems.- Industrial Aspects of Olefin Metathesis/Polymerization Catalysts.- Syntheses of Heterogeneous, Bimetallic Metathesis Catalysts by Reactions of Fischer Type Carbene and Carbyne Complexes with Reduced Phillips Catalyst.- New Results on Alkene Metathesis and Alkyne Polymerisation with Heterogeneous Carbene Tungsten(VI) Complexes.- Aqueous Ring-Opening Metathesis Polymerizations of 7-Oxa-norbornene Derivatives Using Ruthenium Catalysts.- The Application of Ring Opening Metathesis Polymerization to the Synthesis of Substituted Polyacety lenes.- Raman Spectroscopy of Surface Rhenium Oxide on Alumina, Silica, Titania, Niobia and Magnesia.- Raman Spectroscopy of Chromium Oxide Supported on Alumina, Titania and Silica: A Comparative Study.- Stoichiometric and Catalytic Carbene Complex Reactions with the Reduced Phillips Catalyst.- Metathesis-Like Reactions of Heteroalkenes and Heteroallenes with the Carbyne Complex Cl3(dme)W=CCMe3.- Catalytic Metathesis of Alkynes.- Electrochemical Synthesis of Catalytic Species for Alkene Metathesis.- Chromium Supported Catalysts for Ethylene Gas Phase Polymerization.- Metathetical Degradation of Sulfur Vulcanized Polybutadiene by W(CO)6/CCl4/hV.- Photocatalytic Ring-Opening Polymerization of Norbornene and Norbornadiene and Cyclopentene.