Ferrocene-containing ligand systems.

摘要

Chapter 1. Preparation of 1,1′-diaminoferrocene from 1,1′-diazidoferrocene is described. Both ferrocene derivatives were characterized by 1H NMR spectroscopy, X-Ray crystallography and electrochemistry. Reversible 1-electron oxidation of diaminoferrocene led to the isolation and structural characterization of a 17-electron diaminoferrocenium cation. Additionally, the study of thermal properties of diazidoferrocene using Thermogravimetric Analysis and Differential Scanning Calorimetry is discussed.; Chapter 2. Preparation of a silylated diaminoferrocene is described. The compound was used in the synthesis of a Ti dimethyl complex Fc(NSiMe₃)₂TiMe₂. Studies of the activation of this species for olefin polymerization are presented. The structure of a cationic complex featuring an abnormally short Fe-Ti distance is discussed.; Chapter 3. The synthesis of a Zr dibenzyl complex Fc(NSiMe ₃)₂ZrBn₂ is presented. Activation of this complex for olefin polymerization using Lewis acidic reagents was studied in solution and in solid-state. Polymerization of olefins by the resulting cationic species is discussed, including observation of a rare single-insertion species. Activation of the dibenzyl complex with [Ph₃C][B(C₆F₅) ₄] produced an active ethylene polymerization initiator.; Chapter 4. Arylated diaminoferrocenes were obtained using a Pd-catalyzed coupling reaction. The mesityl-substituted derivative served as a ligand for the synthesis of a Zr dibenzyl complex Fc(NMes) ₂ZrBn₂. Abstraction of a benzyl group by B(C₆F ₅)₃ produced a cationic LZrBn+ complex capable of a single insertion of ethylene. Thermally induced CH activation of the dibenzyl complex is discussed.; Chapter 5. Synthesis of ferrocene diimine Fc(N≡CHPh) ₂ is presented. A highly selective reduction of this compound with MeLi afforded diamine Fc[NCH(Me)(Ph)]₂ as the racemic trans diastereomer. This diamine was used in the synthesis of a C ₂-symmetric Zr dibenzyl complex. An analogous Zr dibenzyl complex was prepared as a mixture of diastereomers by a direct reaction between ferrocene diimine and ZrBn₄.; Chapter 6. Starting from 1,1′diaminoferrocene, a series of salen analogs were obtained through condensation with salicylaldehydes. A range of transition metal complexes based on these ligands is reported, including complexes of lanthanum, Group 4 metals, as well as Mn(II), Fe(II), Co(II) and Ni(II) complexes. Several of these compounds were characterized in the solid-state using X-Ray diffraction.