(Montana State University - Bozeman, College of Letters & Science, 2019) Giroux, Michael James; Chairperson, Graduate Committee: Sharon Neufeldt
An analysis of kinetics related to the selectivity of aryldimethylphosphine-nickel complexes for reaction at carbon--chlorine versus carbon--tosylate bonds is reported. A series of aryldimethylphosphine ligands bearing electronically-varied substituents were investigated. The rate constants for oxidative addition of ligand-nickel complexes to either aryl chloride or aryl tosylate substrates were calculated. These rate constants were used to construct Hammett plots describing the susceptibility of oxidative addition at both types of electrophiles to electronic influence from the ligand. Oxidation of catalyst to aryl tosylates yields a plot with a negative slope, while addition to aryl chlorides produces a positive slope. With this, we see that electron donating groups accelerate the addition of catalyst to aryl tosylates, while electron withdrawing groups may change the rate determining step of addition to aryl chlorides.
