Mechanistic and Kinetic Studies of α-Olefin Oligomerization and Selective Ethylene Trimerization

In spite of the reputation of homogenous transition metal catalyzed olefin polymerization to be a mature area of research and a massive industrial success, there still exist knowledge gaps concerning the control of, for example, the polymer molecular weight. This is primarily due to lack of understanding of the catalytic active sites as well as reaction kinetics. The work described in this dissertation is the culmination of the author’s attempts to understand the behavior of selected olefin oligomerization catalysts whose kinetic behaviors were not well understood in previous work reported in the literature. Comprehensive spectroscopic and kinetic studies have led the author to 1) identify hitherto unrecognized tandem catalytic reactions (Chapter 2), 2) introduce new catalysts that exhibit excellent product selectivities (Chapter 3), and 3) determine the elementary-step-specific rate constants for an experimentally challenging oligomerization reaction (Chapter 5)