Olefin polymerization catalysts based on highly electrophilic cobalt(III) complexes: Mechanistic studies and catalyst design

Chapter I reviews the current knowledge of Ziegler-Natta systems for the polymerization, oligomerization, and dimerization of olefins and also provides background on the agostic Co(III) catalysts for ethylene polymerization studied in this dissertation. The review section covers both early and late transition metal-based systems and is followed by a mechanistic discussion with an emphasis on the details of the chain propagation step. In the background section a structural and dynamic analysis of the Co catalyst is presented.;Chapter II details an extensive investigation of the mechanism and kinetics of ethylene polymerization by Cp*(P(OMe);Chapter III describes the design of stabilized Co catalysts through the use of inert counterions. Studies which identify the decomposition pathways in Cp*(P(OMe);Chapter IV describes the oligomerization of 1-hexene and the copolymerization of 1-hexene and ethylene using the stabilized Co catalyst. A mechanism is proposed for the oligomerization reaction and analysis of the copolymer is given. The rate of...