Nuclearity and π-π Interaction Effects on Olefin Polymerization and Coordination Chemistry

Abstract

This thesis details work performed on the use of secondary coordination sphere effects to impact olefin polymerization activity and tacticity control and the coordination chemistry of Y, Fe, and Cu. Chapter One provides a general introduction and summary of each chapter. Chapter Two describes work in collaboration with KFUPM on nuclearity effects in Zr bisamine bisphenolate complexes. Chapter Three describes the coordination chemistry of arene-appended Y di(pyridyl) pyrrolide complexes and the olefin polymerization activity of tris(dimethylamido) Ti, Zr, and Hf di(pyridyl) pyrrolide complexes. Appendix A describes the effects of bulky trialkylsilyl, triphenylsilyl, and diphenyl(alkyl)silyl substituents on the tacticity control of monozirconium amine bis(phenolate) complexes in 1-hexene polymerization. Appendix B describes the synthesis and structures of miscellaneous dizirconium amine bis(phenolate) complexes which could not be isolated in sufficient purity for olefin polymerization tests. Appendix C describes the synthesis, electrochemistry, and reduction of mesityl-substituted di(pyridyl) NHC supported Fe complexes. Appendix D describes the preparation, solid-state structures, and electrochemistry of di(pyridyl) pyrrolide and di(pyridyl) NHC Cu(I) and Cu(II) complexes displaying π-π interactions in the solid state. Appendix E describes work towards the synthesis of di(pyridyl) guanidinate proligands and metal complexes supported by di(pyridyl) urea, monopyridyl and di(pyridyl) N-heterocyclic olefin and N-heterocyclic vinylidene ligands for use in Lewis acid assisted olefin polymerization. Appendix F includes relevant spectra.