Date of Graduation
Eberly College of Arts and Sciences
Jeffrey L. Petersen.
New synthetic routes for the preparation of five-coordinate zirconium and titanium complexes featuring tridentate diamidoamine ligands were developed. Zirconium dichloride complexes, [(Mes)N(CH2)2NR(CH 2)2N(Mes)]ZrCl2 (R=H, SiMe3), were synthesized via a one step toluene elimination reaction. Analogous titanium dichloride complexes, [(Mes)N(CH2)2NR(CH2) 2N(Mes)]TiCl2 (R=H, SiMe3), were prepared using a one-step amine elimination reaction.;The NMR data for all four of the [(Mes)N(CH2)2NR(CH 2)2N(Mes)]MCl2-type complexes demonstrated that they exhibit CS symmetry in solution, as indicated by the observation of six carbon resonances for the aryl carbons and three 1H and 13C NMR resonances for the methyl groups of the mesityl substituents. Molecular structures obtained from crystals of [(Mes)N(CH 2)2NH(CH2)2N(Mes)]ZrCl2 and [(Mes)N(CH2)2N(SiMe3)(CH2) 2N(Mes)]MCl2 (M=Zr, Ti) confirmed the identity of the five-coordinate zirconium and titanium dichloride complexes. The bond angles about the zirconium or titanium atom in the respective complexes indicate that they adopt a geometry that is consistent with the fac structure.
Morgan, Alicia R., "Synthesis and characterization of group IV metal complexes featuring tridentate diamidoamine ligands" (2002). Graduate Theses, Dissertations, and Problem Reports. 1559.