Single Titanocene Preparation And Crystal Structure Analysis

Basing on the variety bonding patterns and the space structure in chemistry theory, organometallic chemistry has become one of the fast development subject and a cross field of many research fields. As to titanocene complexes, especially mono-titanocene complexes, due to their potential as precursors for highly active and selective polymerization catalysts, antitumour drugs, have gotten great interesting in recent yesrs.As one kind of typical metalocene complexes, mono-Cp titanocene complexes are usually used in the fields of science research, chemical engineering and medical treatment. Therefore, the reseach of the synthesis, chemical structure and the properties of the mono-titanocene might provide necessary data and basic theories about their physiologically activity and catalysis. In order to study further the hydrolysis of the mono-Cp titanocene, CpTiCl₃ was used as a raw material to be hydrolyzed completely and obtained two complexes. The structures of the complexes were characterized by single-crystal X-ray analysis, elemental analysis, IR and 'HNMR spectra. The main contents of this dissertation are as follows:1. Two complexes were synthesized, which the structural formula were bis-(cyclopentadienyl) titaniu dichloride (Cp₂TiCl₂) and cyclopentadienyltitanium trichloride (CpTiCl₃). Two mono-Cp titanocene, (CpTiCl₂)₂O and Cp₄Ti₄Cl₄(μ-O)₄, were synthesized by the hydrolysis of CpTiCl₃. The single-crystal X-ray diffraction analysis of Cp₄Ti₄Cl₄(μ-O)₄ suggested that Cp₄Ti₄Cl₄(μ-O)₄ was the multinuclear forms and geometries at titanium atoms were distorted tetrahedrons and the coordinate numbers are four. Each titanium atom is coordinated by one Cl atom, one cyclopentadienyl group and two O atoms, and then form an eight-membered ring linked by oxy-bridges.2. Based on the reaction between CpTiCl₃ and 5-chlorosalicy acid, the titanium complex [Ti(O,O')(5-Cl-OCC₆H₃)₂]·Et₃N was gained. The X-ray diffraction analysis of the complex showed that the mononuclear forms of Ti^IV and the titanium atom is coordinated by two 5-chlorosalicy acid through their oxygen atoms of hydroxyl and carboxyl oxygen atoms. Each 5-chlorosalicy acid acts as a bidentate ligand and coordinates with Ti^IV to form hexacyclic ring, respectively.In addition, the reaction between Cu(NO₃)₂·3H₂O and 3-Nitrophthalic acid and 2,2'-Bipyridyl in EtOH/H₂O solution gave a biligand dinuclear complex [Cu₂(C₈H₃NO₆)₂ (C₁₀H₈N₂)₂(H₂O)₂]·2H₂O (C₈H₃NO₆ = 3-Nitrophthalate, C₁₀H₈N₂ = 2,2'-Bipyridyl). The complex was characterized by elemental analysis, IR spectra. The single crystal X-ray diffraction analysis reveals the complex crystals in the triclinic P-1 space group.