Synthesis and characterization of group IV metal complexes featuring tridentate diamidoamine ligands

Abstract

New synthetic routes for the preparation of five-coordinate zirconium and titanium complexes featuring tridentate diamidoamine ligands were developed. Zirconium dichloride complexes, [(Mes)N(CH 2) 2 NR(CH 2) 2 N(Mes)]ZrCl 2 (R = H, SiMe 3), were synthesized via a onestep toluene elimination reaction. Analogous titanium dichloride complexes, [(Mes)N(CH 2) 2 NR(CH 2) 2 N(Mes)]TiCl 2 (R = H, SiMe 3), were prepared using a one-step amine elimination reaction. Table of Contents iv List of Tables vi List of Figures vii Chapter 1. Introduction 1 Chapter 2. Results and Discussion 2.1. Preparation and Characterization of Triamines (Mes)NH(CH 2) 2 NR(CH 2) 2 NH(Mes), R = H, SiMe 3 2.2. Preparation and Characterization of Five-Coordinate Zirconium Complexes 2.3. Preparation and Characterization of Five-Coordinate Titanium Complexes 2.4. Description of the Crystal Structures of 10, 11, and 13 Chapter 3. Concluding Remarks Chapter 4. Experimental Section 4.1. Reagents 4.2. General Considerations 4.3. Preparation of Starting Materials 4.3.1. Preparation of Zr(NMe 2) 4 , 1 4.3.2. Preparation of Ti(NMe 2) 4 , 2 4.3.3. Preparation of Ti(NMe 2) 2 Cl 2 , 3 4.3.4. Preparation of LiNEt 2 , 4 4.3.5. Preparation of Ti(NEt 2) 4 , 5 4.3.6. Preparation of Ti(NEt 2) 2 Cl 2 , 6 4.4. Preparation of Triamines (Mes)NH(CH 2) 2 NR(CH 2) 2 NH(Mes), R = H, SiMe 3 4.4.1. Preparation of (Mes)NH(CH 2) 2 NH(CH 2) 2 NH(Mes), Mes = Mesityl, 7 4.4.2. Preparation of (Mes)NH(CH 2) 2 N(SiMe 3)(CH 2) 2 NH(Mes), Mes = Mesityl, 8 4.5. Preparation of Five-Coordinate Zirconium Bis(dimethylamido) Complexes v 4.5.1. Preparation of [(Mes)N(CH 2) 2 NH(CH 2) 2 N(Mes)]Zr(NMe 2) 2 , Mes = Mesityl, 9 4.6. Preparation of Five-Coordinate Zirconium Dichloride Complexes 4.6.1. Preparation of [(Mes)N(CH 2) 2 NH(CH 2) 2 N(Mes)]ZrCl 2 , Mes = Mesityl, 10 4.6.1.1. Reaction of 9 with SiMe 3 Cl 4.6.1.2. Toluene Elimination Reaction 4.6.2. Preparation of [(Mes)N(CH 2) 2 N(SiMe 3)(CH 2) 2 N(Mes)]ZrCl 2 , Mes = Mesityl, 11 4.7. Preparation of Five-Coordinate Titanium Dichloride Complexes 4.7.1. Preparation of [(Mes)N(CH 2) 2 NH(CH 2) 2 N(Mes)]TiCl 2 , Mes = Mesityl, 12 4.7.1.1. Amine Elimination Reaction with 3 4.7.1.2. Amine Elimination Reaction with 6 4.7.2. Preparation of [(Mes)N(CH 2) 2 N(SiMe 3)(CH 2) 2 N(Mes)]TiCl 2 , Mes = Mesityl, 13 4.8. Description of the X-ray Structural Analyses Chapter 5. References Vita