Study On Synthesis And Reaction Of Hetero Nucleus Titanocene Complexes Containing Ferroenyl Group In Mild Condition

Titanocene derivatives have received considerable attention due to their potential as highly active and selective polymerization catalyst precursors, hydrogenation and isomerization, anti-tumour and anti-oxidative action. In this dissertation, the syntheses of titanocene derivatives are reviewed, especially in water or two phase system. The syntheses of titanocene complexes containing ferroenyl group were also reviewed. A series of ligands and tianocene complexes bearing phenylferrocene have been prepared and characterized. The main results of this dissertation are shown as follows:1. Dichloride titanocene and dimethylcyclopentadienyl dichlorotitanium were prepared by using titanium tetrachloride, dicyclopentadiene, and dimethylcyclopenta -diene as raw materials. Compounds 5-ferrocenyl-2-hydroxylbenzoic acid, 2-ferrocenylbenzoic acid and 4-ferrocenylbenzoic acid were prepared by using the following: ferrocene, 5-aminosalisylic acid, 2-aminobenzoic acid and 4-aminobenzoic acid respectively. 4-ferrocenylbenzoic acid was prepared according to the modified procedure. In the meantime, two alkyl ferrocenyl complexes, 5-ethylferrocenyl -2-hydroxylbenzoic acid and 5-diethyl- ferrocenyl-2-hydroxylbenzoic acid were synthesized by reacting ethylferrocene/diethylferrocene and 5-aminosalisylic acid. All of complexes were characterized by IR and ¹H NMR spectra.2. A new complex was prepared by "one-pot" method from ferrocene, phosphorus trichloride and 4-aminosalicylic acid, which was characterized by UV-vis, elemental analysis IR, ¹H NMR and single-crystal X-ray analysis. Crystallographic characterization of the new complex shows that the crystal is in the triclinic system, space group P1 with a = 5.954(2) A, b = 13.208(5) A, c = 13.252(5) A, α = 60.993(7) A, β = 84.342(8)°, γ = 86.933(8)°, V = 906.8(6) A³, Dc = 1.601 g/cm3, Z - 2, μ= 0.987 mm^-1, F(000) = 452, R₁ = 0.0647, wR₂ = 0.1333.3. Two new titanocene complexes containing a ferrocenyl group were prepared in two-phase media by the reaction of titanocene dichloride/dimethylcyclopentadienyl dichlorotitanium with 5-ferrocenyl-2-hydroxyl-benzoic acid in the presence of acetylace -tone/5-sulfosalicylic acid under mild conditions. The compounds were characterized by UV-vis, elemental analysis, IR, ¹H NMR and X-ray diffraction analyses. Based on theUV-vis spectrum the reaction process was also studied. Single X-ray diffraction analyses show that the conformation of two cyclopentadienyl rings bonding iron change from eclipsed conformer to staggered conformer while methyl groups link to the other two cyclopentadienyl rings of the molecule.4. Two titanocene complexes containing a ferrocenyl group were characterized by X-ray diffraction analyses. The results show that the crystal of (5-ferrocenyl-2-hydroxy -benzenecarboxylato-OjOOtitanoceneCIV) is monoclinic of space group P2i/c, the cell parameters are as follows: a = 13.752(4) A, b = 12.180(4) A, c = 12.468(3) A, a - 90°, P = 92.42(2)°, 7 = 90°, V = 2086.4(10) A3, Dc = 1.586 g/cm3, Z = 4, u = 0.776 mm"1, F(000) = 1024, Ri = 0.0643, wR2 = 0.1288. The crystal of dimethylcyclopentadienyl 5-ferrocenylsalicylatotitanium(rV) is monoclinic of space group P2i/c, the cell parameters are as follows: a = 14.3310(9) A, b = 12.5065(8) A, c = 12.9406(10) A, a = 90°, p = 95.101(4)°, y = 90°, V = 2310.2(3) A3, Dc = 1.513 g/cm3, Z = 4, n = 0.900 mm'1, F(000) = 1088, R, = 0.0461, wR2 = 0.1048.