Tetrabenzo[a,c,g,i]fluorenyltitanium(III) and -(IV) complexes: Syntheses, reactions, and catalytic application
Tetrabenzo[a,c,g,i]fluorenyltitanium(III) and -(IV) complexes: Syntheses, reactions, and catalytic application
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四苯并[a,c,g,i]芴基钛(III)和-(IV)配合物：合成、反应和催化应用
DOI：
10.1021/om7012293
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发表时间：
2008
期刊：
影响因子：
2.8
通讯作者：
A. Lützen
中科院分区：
文献类型：
--
作者：
K. Schröder;D. Haase;W. Saak;R. Beckhaus;W. P. Kretschmer;A. Lützen
四苯并[a，c，g，i]荧基锂[TbfLi(Thf)4(1)}与TiCl3(Thf)3(2)反应生成η5-四苯并[a，c，g，i]荧钛(III)衍生物TbfTiCl2(Thf)(3)，通过四氯甲烷氧化氯化可将其转移到钛(IV)配合物TbfTiCl3(4)上。TbfTiCl2(OAr)(Ar=4-tBuC6H4(5)，2，6-Me2C6H3(6)，2，4，6-Me3C6H2(7)，2，6-iPrC6H3(8)，2，6-Ph2C6H3(9))。此外，3与自由基或自由基生成的过氧化氢反应生成TbfTiCl2TEMPO(10)和TbfTiCl2OtBu(11)。所有化合物均经红外光谱、质谱学、核磁共振仪和X-射线单晶学进行了表征。最后，用d-MAO对化合物6、8、9和10进行了乙烯聚合实验。其活性按如下顺序增加：[Kg(PE)−1h−1bar−1]：6(320)<；8(320)<；10(760)<；9(1000)
Reacting tetrabenzo[a,c,g,i]fluorenyllithium {TbfLi(THF)4(1)} with TiCl3(THF)3(2) leads to the formation of the η5-tetrabenzo[a,c,g,i]fluorenyltitanium(III) derivative TbfTiCl2(THF) (3), which can be conveyed to the titanium(IV)complex TbfTiCl3(4) by oxidative chlorination with CCl4. Subsequent reaction with various lithium phenoxides gives a series of titanium complexes of the type TbfTiCl2(OAr) (Ar = 4-tBuC6H4(5), 2,6-Me2C6H3(6), 2,4,6-Me3C6H2(7), 2,6-iPrC6H3(8), 2,6-Ph2C6H3(9)). Furthermore,3was reacted with radicals or radical-generating peroxides to form the complexes TbfTiCl2TEMPO (10) and TbfTiCl2OtBu (11). All compounds were characterized by IR, MS, and NMR measurements and X-ray crystallography. Finally, compounds6,8,9, and10were subjected to ethylene polymerization experiments using d-MAO. The activities increase in the following order [kG(PE)mol(Ti)−1h−1bar−1]:6(320) <8(320) <10(760) <9(1000).