新型限制几何构型茂金属化合物的试合成研究
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摘要
本文采用不同的方法合成了5种富烯,尝试以6,6-二苯基富烯、6,6-二甲基富烯为原料一锅法合成新型(sp3-C1)桥联CGC。合成产物通过1H NMR、MS、IR进行了分析,发现产物中有目标络合物存在,即{[(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)}。以6,6-二苯基富烯为原料采用一锅法合成(sp3-C1)桥联CGC络合物C1,没有发现叔丁胺基锂与富烯环外双键加成时发生α-攫氢反应。利用6,6-二甲基富烯与大位阻胺基锂(PhNHLi、C6H11NHLi)反应合成C2和C3,质谱及核磁结果表明反应过程中有胺基锂与少量富烯发生α-攫氢反应,最终产物中含有二氯二(异丙烯基环戊二烯基)钛化合物。在合成C2时考察了加料反应温度、溶剂、时间对产率的影响；当以混合溶剂Hexane-THF(4:1),在加料温度-78℃反应2 h,自然升至室温,反应72h,产率最高可达67%。
尝试以甲氧乙基环戊二烯为原料通过简单的一步法合成侧链含氧型CGC,没有成功。对产物进行了1H NMR、13C NMR、HRMS、IR表征和结构解析,发现得到了2个取代二茂络合物{[(η5-C5H4CH2CH20CH3)]2TiCl2(C4), [(η5-C5H4CH2CH20CH3)]2ZrCl2 (C5)}。在合成络合物C4和C5时,发现当CH30CH2CH2CpNa与TiCl4物质的量比例小于等于2时反应产物为C4；同样的条件下配体的钠盐与ZrCl4反应得到C5。
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.
尝试以甲氧乙基环戊二烯为原料通过简单的一步法合成侧链含氧型CGC,没有成功。对产物进行了1H NMR、13C NMR、HRMS、IR表征和结构解析,发现得到了2个取代二茂络合物{[(η5-C5H4CH2CH20CH3)]2TiCl2(C4), [(η5-C5H4CH2CH20CH3)]2ZrCl2 (C5)}。在合成络合物C4和C5时,发现当CH30CH2CH2CpNa与TiCl4物质的量比例小于等于2时反应产物为C4；同样的条件下配体的钠盐与ZrCl4反应得到C5。
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.
引文
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