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首页> 外文期刊>Organometallics >Aryloxy Alkyl Magnesium versus Dialkyl Magnesium in the Lanthanidocene-Catalyzed Coordinative Chain Transfer Polymerization of Ethylene
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Aryloxy Alkyl Magnesium versus Dialkyl Magnesium in the Lanthanidocene-Catalyzed Coordinative Chain Transfer Polymerization of Ethylene

机译：芳氧基烷基镁与二烷基镁在乙烯的镧系催化协调环转移聚合中

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摘要

Complexes [(1,2,4-Ph3C5H2)(2)NdCl2K(THF)(2)](2) (Nd1), {[1,2-Ph-2-4-(4-MeOC6H4)C5H2](2)NdCl2K(THF)(2)}(2) (Nd2), {[1,2-Ph-2-4-(2-MeO-C6H4)C5H2](2)NdCl2[K(THF)(4)]}-(THF)(0.5) (Nd3), and [(1,2,4-Ph3C5H2)(2)TbCl2K](2) (Tb1) have been synthesized, studied by X-ray diffraction analysis, and used in coordinative chain transfer polymerization (CCTP) of ethylene upon activation by alkyl magnesium derivatives. The complexes Ndl and Tbl exhibiting similar molecular structures and the same core type have demonstrated similar catalytic activities. Two types of alkylating/chain transfer agents, namely, di-n-butyl magnesium and heteroleptic complex (BHT)Mg(THF)(2)Bu-n Mg1 (BHT = 2,6-di-tert-butyl-4-methylphenoxide), have been studied in this reaction. We have found that (BHT)Mg(PE) products (PE is an oligoethylene chain) are being formed at a relatively high rate while using Mgl at 40 degrees C in the solution polymerization of ethylene; the oligomeric products comprise more than 40 ethylene fragments, unlike Mg(PE)(2) derivatives, which are obtained from (MgBu2)-Bu-n and contain about 20 ethylene fragments. Luminescence spectroscopy study of the reaction mixtures, while initiating the complex Tb 1 by (MgBu2)-Bu-n or Mg1, confirmed the structural proximity and high symmetry of the catalytic complexes for both types of Mg reagents. These experimental results reaffirmed the hypothesis about the CCTP mechanism, suggesting the formation of trinuclear LnMg(2) catalytic species. Within this mechanism, we can explain the increase in the polymerization degree (P-n) when Mg1 is used by growing a single oligoethylene chain (PE) per a Mg atom to form (mu-BHT)(2)Mg-2(PE)(2) species, whereas application of (MgBu2)-Bu-n provides the growth of two PE chains to form the Mg-2(PE)(4) product with lower solubility.
机译：复合物[（1,2,4-PH3C5H2）（2）NdCl 2K（THF）（2）]（2）（2）（ND1），{[1,2-pH-2-4-4-（4-Meoc6H4）C5H2]（2 ）NdCl 2K（THF）（2）}（2）（ND2），{[1,2-pH-2-4-（2-MeO-C6H4）C5H2]（2）NdCl2 [K（THF）（4）]已经合成了X射线衍射分析研究，并在协调中合成} - （THF）（0.5）（ND3）和[（1,2,4-pH3C5H2）（2）TBCL 2K]（2）（2）（TB1），并用于协调烷基镁衍生物激活后乙烯链转移聚合（CCTP）。络合物NDL和TBL表现出类似的分子结构和相同的核心类型表现出类似的催化活性。两种类型的烷基化/链转移剂，即，二正丁基镁和杂络合物（BHT）的Mg（THF）（2）步正MG1（BHT = 2,6-二叔丁基-4-甲基苯酚的），已经在这种反应中进行了研究。我们发现（BHT）Mg（PE）产物（PE是寡核链）以相对高的速率在乙烯的溶液聚合中在40℃下使用MGL;寡聚产物包含40多个乙烯片段，与Mg（PE）（2）衍生物不同，其由（MgBu2）-Bu-N获得并含有约20个乙烯片段。反应混合物的发光光谱研究，同时通过（MGBU2）-Bu-n或Mg1引发复合Tb1，证实了两种类型的Mg试剂的催化配合物的结构接近和高对称性。这些实验结果重申了关于CCTP机制的假设，表明三核LNMG（2）催化物种的形成。在该机制内，当通过每镁原子生长单个寡聚糖链（PE）形成（MU-BHT）（2）Mg-2（PE）（PE）时，我们可以解释聚合度（PN）的增加。 2）物种，而应用（MgBu2）-Bu-N提供了两个PE链的生长，形成所述Mg-2（PE）（4）产物具有较低的溶解度。

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