Computational studies into transition metal catalyzed cross-coupling reactions

This thesis discusses mechanistic aspects of transition metal catalyzed cross-coupling reactions. Improved methods for quantifying sterics in a transition metal complex are presented in Chapters 2 and 3 with the exact cone angle and the exact solid angle. These methods provide insight into the role sterics play in such catalytic complexes. Additionally, as these methods can use computationally obtained structures to quantify sterics, a change in sterics can be tracked over the course of a reaction to further understand the dynamics of transition metal complexes. Chapters 47 details mechanistic properties of two popular cross-coupling methods, Kumada and Stille cross-coupling, which can be modified for the synthesis of conjugated polymers. Of particular interest is the oxidative addition step in the reaction cycle, discussed in Chapters 57, which must occur through an intramolecular insertion method for polymerizations to be chain-growth in character and produce polymer of controlled molecular weight and narrow dispersity.