| Two major topics are covered: the first chapter is focused on the development of post-metallocene complexes for propylene polymerization. The second and third chapters investigate the consequences of diisobutylaluminum hydride (HAliBu2) additives in zirconocene based polymerization systems. The synthesis, structure, and solution behavior of early metal complexes with a new tridentate LX2 type ligand, bis(thiophenolate)pyridine ((SNS) = (2-C6H4S)2-2,6-C5H3N) are investigated. SNS complexes of Ti, Zr, and Ta having dialkylamido coligands were synthesized and structurally characterized. The zirconium complex, (SNS)Zr(NMe2)2, displays C2 symmetry in the solid state. Solid-state structures of tantalum complexes (SNS)Ta(NMe2)3 and (SNS)TaCl(NEt2)2 also display pronounced C2 twisting of the SNS ligand. 1D and 2D NMR experiments show that (SNS)Ta(NMe2)3 is fluxional with rotation about the Ta N(amide) bonds occurring on the NMR timescale. The fluxional behavior of (SNS)TaCl(NEt2)2 in solution was also studied by variable temperature 1H NMR. Observation of separate signals for the diastereotopic protons of the methylene unit of the diethylamide indicates that the complex remains locked on the NMR timescale in one diastereomeric conformation at temperatures below 50 °C. Reduction of Zr(IV) metallocenium cations with sodium amalgam (NaHg) produces EPR signals assignable to Zr(III) metallocene complexes. Thus, chloro-bridged heterobinuclear ansa-zirconocenium cation [((SBI))Zr(-Cl)2AlMe2]+B(C6F5)4 (SBI = rac-dimethylsilylbis(1-indenyl)), gives rise to an EPR signal assignable to the complex (SBI)ZrIII(&... |
