Study Of Attempting To Synthesize Novel Constrained Geometry Metallocene Compounds

Five fulvene were synthesized by different method in this paper. Attempted to synthesize novel (sp3-C1)-bridged CGC compounds by starting compounnds of 6,6-diphenylfulvene and 6,6-dimethylfulvene. Complexes were characterized and analyzed by 1H NMR, MS and IR, The results indicated that the products contained the expected complex respectively {[(η5-C5H4)(C6H5)2C(η1-NCMe3)]ZrCl2(C1),[(η5-C5H4)(CH3)2C-(η1-N(C6H5))]TiCl2(C2);[(η5-C5H4)(CH3)2C(η1-N(C6H11))]TiCl2(C3)}. It was found that in the process of one pot synthesizing (sp3-C1)-bridged CGC (C1), the reaction ofα-H removing in 6,6-diphenyl-fulvene didn't happened. C2 and C3 were synthesized by 6,6-dimethylfulvene reacting with bulky aminolithium(PhNHLi, C6H11NHLi), The result of MASS and 1H NMR indicated that a small part of dichlorid di(iso-propenylcyclopentadienyl)titanocene was formed because ofα-H removing reaction. The effect of feeding reaction temperature, solvent and time on yield for C2 were studied, optimum reaction condition was obtained:when solvent was hexane/ THF(4:1), the feeding temperature was -78℃for 2 hours, then the temperature rised to r.t.naturally, reaction time was 72 hours, the highest yield was 67%.Attempted to synthesize the type of titanium(zirconium) oxygen heterocyclic CGC compounds by simple one step synthetic method using methoxyethylcyclopentadien was unsuccessful. The products were well characterized by 1H NMR,13C NMR, HRMS and IR, and results showed that two substituted dicyclopentadienyl complexes{[(η5-C5H4CH2CH2O-CH3)]2TiCl2(C4),[(η5-C5H4CH2CH2OCH3)]2ZrCl2 (C5)} were obtained. When the ratio of CH3OCH2CH2CpNa and TiCl4 was less than or equal 2:1, the product was C4. C5 was obtained in the same condition by CH3OCH2CH2CpNa reacting with ZrCl4.