A general one-pot synthesis for elusive 2-substituted indenes: does bis[2-(tert-butyl)indenyl]zirconium(IV)dichloride/MAO polymerise ethene?

Moller AC; Blom R; Heyn RH; Swang O; Kopf JU; Seraidaris T

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A general one-pot synthesis for elusive 2-substituted indenes: does bis[2-(tert-butyl)indenyl]zirconium(IV)dichloride/MAO polymerise ethene?

机译：难以捉摸的2-取代的茚的一般一锅合成：双[2-（叔丁基）茚基]二氯化锆（IV）/ MAO是否能使乙烯聚合？

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Among the 2-substituted indenes, 2-trifluoroindene and 2-tert-butylindene are poorly or incompletely described in the open literature. We herein describe an efficient one-pot synthesis of these compounds as a variation of the Perkin reaction which allows us to refute an earlier claim that bis(2-tertbutylindenyl) zirconium(IV) dichloride (2a) will not polymerise ethene. In fact, 2a/MAO polymerises ethene to extremely high molecular weights. Extensive DFT calculations on the polymerisation mechanism revealed an unprecedented suppression of the otherwise predominant chain termination by beta-hydride transfer due to steric congestion of the active site.

机译：在2-取代的茚满中，在公开文献中很少或不完全描述2-三氟茚和2-叔丁基茚。我们在本文中描述了这些化合物的有效一锅合成，作为珀金反应的一种变化，这使我们可以驳斥一个较早的主张，即双（2-叔丁基茚基）二氯化锆（IV）（2a）不会聚合乙烯。实际上，2a / MAO可将乙烯聚合成极高的分子量。关于聚合机理的大量DFT计算显示，由于活性位的空间拥塞，β-氢化物转移对其他主要的链终止反应产生了空前的抑制作用。

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来源
《Dalton transactions: An international journal of inorganic chemistry》 |2006年第17期|共8页
作者
Moller AC; Blom R; Heyn RH; Swang O; Kopf JU; Seraidaris T;
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正文语种 eng
中图分类无机化学;
关键词
D(0)F(N) TRANSITION-METALS; ETHYLENE POLYMERIZATION; ELASTOMERIC POLYPROPYLENE; METHYLALUMINOXANE MAO; OLEFIN POLYMERIZATION; UNIFIED VIEW; MOLECULAR CALCULATIONS; ZIRCONOCENE COMPLEXES; NMR; CATALYSTS;

机译：D（0）F（N）过渡金属;乙烯聚合;弹性聚丙烯;甲基铝氧烷毛;烯烃聚合;统一视角;分子计算;锆茂配合物;NMR;催化剂;

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1. A general one-pot synthesis for elusive 2-substituted indenes: does bis[2-(tert-butyl)indenyl]zirconium(IV)dichloride/MAO polymerise ethene? [J] . Moller AC, Blom R, Heyn RH, Dalton transactions: An international journal of inorganic chemistry . 2006,第17期

机译：难以捉摸的2-取代的茚的一般一锅合成：双[2-（叔丁基）茚基]二氯化锆（IV）/ MAO是否能使乙烯聚合？
2. Synthesis,structure,and ethene polymerisation catalysis of 1-or 2-silyl substituted bis[indenyl]zirconium(iv)dichlorides [J] . Andreas C.Moller, Richard H.Heyn, Richard Blom, Dalton transactions: An international journal of inorganic chemistry . 2004,第10期

机译：1-或2-甲硅烷基取代的双[茚基]锆（iv）二氯化物的合成，结构和乙烯聚合催化
3. Zirconium bis-indenyl compounds. The influence of substituents on the ethene polymerization behavior of 1-and 2-substituted (R-Ind)(2)ZrCl2/MAO catalysts [J] . Grimmer NE., Coville NJ., de Koning CB. Journal of Organometallic Chemistry . 2002,第1a2期

机译：双茚基锆化合物。取代基对1-和2-取代的（R-Ind）（2）ZrCl2 / MAO催化剂乙烯聚合行为的影响
4. Oligomerization of 1-Butylene to Lubricant Catalyzed by Bis(tetramethyl cyclopentadienyl) Zirconium dichloride/MAO [C] . Meichao Chen, Huaiqi Shao, Tao Jiang International Conference on Chemical, Material and Metallurgical Engineering . 2013

机译：双丁烯对由双（四甲基环戊二烯基）锆二氯甲酸锆催化的1-丁烯的寡聚化物
5. Dichloridobis{2-(dimethylamino)methylphenyl}bis{2-(dimethylazaniumyl)methylphenyl}di-μ-hydroxido-di-μ3-oxido-tetraphenyltetratin(IV) dichloride deuterochloroform decasolvate [O] . Jan Turek, Zdeňka Padělková 2011

机译：二氯二双{2-（二甲基氨基）甲基苯基}双{2-（二甲基氮杂甲基）甲基苯基}二-羟基氢氧化物-二-μ3-氧化-四苯基四锡（IV）二氯十氟氯仿
6. Crystal structures of di-μ-bromido-bis{dibromido[η5-2-(dimethylamino)indenyl]zirconium(IV)} and dibromidobis[η5-2-(dimethylamino)indenyl]zirconium(IV) [O] . Michael G. Medvedev, Ilya S. Borisov, Pavel S. Kulyabin, 2016

机译：二-μ-溴代 - 二{二溴[η5-2-（二甲基氨基）茚基]锆（IV）}和二溴双[η5-2-（二甲基氨基）茚基]锆（IV）的晶体结构

A general one-pot synthesis for elusive 2-substituted indenes: does bis[2-(tert-butyl)indenyl]zirconium(IV)dichloride/MAO polymerise ethene?

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