methylaluminoxane | 124088-77-3

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机过渡后金属化合物
• 英文名称: methylaluminoxane
• 英文别名: MAO；[methylaluminoxane]n；methylalumoxane；methylaluminoxide；monomer of methylaluminoxane；oxymethylaluminum；MeAlO；methyl(oxo)alumane
• CAS: 124088-77-3
• 化学式: AlO*CH₃
• 分子量: 58.0158
• InChiKey: CPOFMOWDMVWCLF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.08
• 重原子数：
  3
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  methylaluminoxane 、 [(2-(C(H)=N(2,6-(i-Pr)2C6H3))-4,6-(t-Bu)2-phenoxide)CuCl]2 以 甲苯 为溶剂， 以95%的产率得到[(2-(C(H)=N(2,6-(i-Pr)2C6H3))-4,6-(t-Bu)2-phenoxide)AlMe2]
  参考文献：
  名称：

  Copper(II) Ethylene Polymerization Catalysts: Do They Really Exist?

  摘要：

  The reactions of two types of copper(II) ethylene polymerization catalysts, [(sal)CuCl](2) (sal = 2-{C(H)=N(2,6-Pr-i(2)-C6H3)}-4,6-Bu-t(2)-phenoxide) and (alpha-diimine)CuCl2 (alpha-diimine = [(2,6-Pr-i(2)-C6H3)-N=C(Me)](2)). with methylaluminoxane (MAO) and trimethylaluminum (TMA) have been investigated. In both examples, facile and irreversible ligand (L) transfer from copper to TMA present in MAO was observed, resulting in formation of the corresponding (sal)AlMe2 and (imino-amido)AlMe2 complexes. The (imino-amido)AlMe2 complex is formed by alpha-diimine ligand transfer to aluminum followed by alkylation of one imino moiety in the ligand backbone. Both aluminum complexes were active catalysts for ethylene polymerization with activities similar to their Cu(II) precursors. Simple addition of a neutral salicylaldimine or alpha-diimine ligand to MAO in the absence of any copper species resulted in the formation of the corresponding LAlMe2 complexes, which are again active for ethylene polymerization. These results indicate that ethylene polymerization does not occur by a migratory insertion mechanism at the copper center, but is the result of ligand transfer to aluminum, and it is the resulting LAlMe2/LAlMe+-complexes that are likely the active species.

  DOI：

  10.1021/om800625f
• 作为产物：
  描述：

  aluminum(III) sulphate octadecahydrate 在 trimethyl aluminum 作用下， 以 甲苯 为溶剂， 以21%的产率得到methylaluminoxane
  参考文献：
  名称：

  Variation of polypropylene microtacticity by catalyst selection

  摘要：

  The polymerization of propylene with use of soluble catalysts derived from rac-(1,2-ethylenebis(eta-5-3-alkylcyclopentadienyl))zirconium dichlorides (rac-1) and their corresponding meso isomers (meso-1), in combination with methylaluminoxane cocatalyst, was studied. The polymerization activity of catalysts derived from compounds rac-1 and meso-1 was somewhat lower than that reported for the well-studied catalysts of this structural type rac-(ethylenebis(eta-5-indenyl)))zirconium and rac-(ethylenebis(eta-5-tetrahydroindenyl))zirconium dichlorides (2 and 3, respectively); however, the degree of microtacticity of the poly(propylene) produced was higher, as determined by C-13 NMR spectroscopy. The polymerization activity of the meso compounds (meso-1) was lower than that of their racemic counterparts. Finally, meso-(ethylenebis(eta-5-tetrahydroindenyl))zirconium dichloride (4) was isolated in pure form as a minor product from the preparation of the racemic isomer. This compound is less active than its racemic diastereomer 3 and produces atactic poly(propylene). Compound 4 was characterized by a single-crystal X-ray diffraction analysis: space group P2(1)/c; Z = 4; a = 12.051 (2) angstrom, b = 15.184 (3) angstrom, c = 9.939 (2) angstrom, beta = 92.94 (1)degrees; V = 1816.3 (5) angstrom 3; R = 0.0256, R(W) = 0.0299 for 2784 unique reflections with I > 3-sigma(I).

  DOI：

  10.1021/om00052a064
• 作为试剂：
  描述：

  [Me2Al(μ-OCPh3)]2 在 methylaluminoxane 作用下， 以 氘代甲苯 为溶剂， 生成 1,1,1-三苯乙烷
  参考文献：
  名称：

  铝醇盐作为合成子为甲基铝氧烷（MAO）：的产品催化热分解[我2的Al（μ-OCPh 3）] 2

  摘要：

  的热分解[我2的Al（μ-OCPh 3）] 2，以获得pH 3 CME和甲基铝氧烷（[MeAlO] Ñ，MAO），最初通过加入阿尔梅的催化3 ; 然而，该反应也被MAO产物催化。总反应速率的形式如下：速率= ķ TMA [{我2的Al（μ-OCPh 3）} 2 ] [阿尔梅3 ] + ķ MAO [{我2的Al（μ-OCPh 3）} 2 ] [MAO]其中ķ MAO » ķ TMA。ΔAlMe 3-和MAO催化的反应的H been分别确定为175±8和190±15 kJ·mol - 1。两种反应均显示出较大的ΔS positive正值（分别为41±8 eu和<53 eu），表明有解离反应。的热分解[我2的Al（μ-OCPh 3）] 2也由路易斯酸，其中包括催化的AlCl 3，氯化铝2 Me和AlClMe 2。在阿尔梅的相对速率的基础3的[我催化的热分解2的Al（μ-OCPh 3）] 2，[Me

  DOI：

  10.1021/om0106128

文献信息

• Me₂AlCH₂PMe₂: A New, Bifunctional Cocatalyst for the Ni(II)-Catalyzed Oligomerization of PhSiH₃
  作者：Frédéric-Georges Fontaine、Davit Zargarian

  DOI：10.1021/ja048911m

  日期：2004.7.1

  (t(1/2) ca. 12 h) but accelerates the Si-H bond activation and Si-Si bond formation reactions. The catalysis promoted by 2a/3 proceeds even faster in the presence of NEt3 or THF (TOF > 1600 h(-1)), because these Lewis bases favor the monomeric form of 3, which in turn favors the formation of 4. On the other hand, the much more nucleophilic base quinuclidine suppresses the catalysis (TOF < 300 h(-1)) by hindering

  已经研究了甲基铝氧烷 (MAO) 在 Ni 催化的 PhSiH3 脱氢同系化中的作用，以设计具有明确定义的化学成分和结构的新型助催化剂。这些研究表明，双功能试剂 (Me2PCH2AlMe2)2, 3 等物质应作为 Si-Si 键形成反应的助催化剂。因此，发现 (1-Me-茚基)Ni(PPh3)Me、2a 和 3（Ni/Al 比率为 1:1）的组合将 PhSiH3 转化为具有转换频率的环状低聚物 (PhSiH)n（ TOF) > 500 h(-1)，比单独使用 2a 快 50 倍。详细的 NMR 研究表明，这种加速是由于中间体 (1-Me-茚基)Ni(Me)(Me2PCH2AlMe2), 4 的形成。该复合物中的 PMe2 部分与 Ni 中心的协调允许系留的 AlMe2 部分与 Ni-Me 部分相互作用，从而促进相当缓慢的 Al-Me/Ni-CD3 交换 (t(1/2) ca。 12 h) 但加速了
• Synthesis, characterization and catalytic activity of the complex titanium bis(dimethylmalonate)–bis(diethylamido) in the polymerization of propylene
  作者：Tal Gueta-Neyroud、Boris Tumanskii、Mark Botoshansky、Moris S. Eisen

  DOI：10.1016/j.jorganchem.2006.10.031

  日期：2007.2

  account we present the synthesis, characterization and catalytic activity in the polymerization of propylene of a bis(dimethyl malonate) titanium bis(diethylamine) complex (1). The complex exhibits in solution a dynamical isomerization following an internal Bailar twist. The activation of complex 1 was obtained by its reaction with methylalumoxane (MAO). The activated complex in solution shows a different

  因此，我们提出了双（丙二酸二甲酯）钛双（二乙胺）配合物（1）在丙烯聚合中的合成，表征和催化活性。该复合物在溶液中表现出内部拜拉尔扭曲后的动态异构化。配合物1通过与甲基铝氧烷（MAO）反应获得活化。在溶液中显示了活化络合物涉及η单齿之间的平衡不同的动态过程1和二齿η 2丙二酸二甲酯配体与金属中心的结合。该平衡负责至少两个用于主要具有对称性差异的聚合反应的活性物质的形成。发现配体的单齿配位（开放形式）是被MAO活化的复合物活性物种的主要形式，最有可能是由于配体中的氧原子与强路易斯酸共催化剂。通过NMR和ESR光谱学研究聚合中的活性物质。所得聚丙烯显示出具有低规整度的弹性体性能。
• Reactions between an Ethylene Oligomerization Chromium(III) Precatalyst and Aluminum-Based Activators: Alkyl and Cationic Complexes with a Tridentate NPN Ligand
  作者：Shaofeng Liu、Roberto Pattacini、Pierre Braunstein

  DOI：10.1021/om200243a

  日期：2011.7.11

  of the nature of the species formed in situ by reaction of a catalyst precursor complex and typical cocatalysts used for ethylene oligomerization or polymerization, the Cr(III) complex fac-[Cr(NPN)Cl3] (1; NPN = bis(2-picolyl)phenylphosphine) was reacted with MAO and partial methylation to give the mononuclear complex fac-[Cr(NPN)Cl2.23Me0.77] (2) was observed, whereas reaction with AlMe3 in toluene

  为了更深入地了解通过催化剂前体配合物与乙烯低聚或聚合反应所用的典型助催化剂反应原位形成的物质的性质，Cr（III）配合物fac- [Cr（NPN）Cl 3 ]（1 ; NPN =双（2-吡啶甲基）苯基膦）与MAO反应并部分甲基化，得到单核络合物fac- [Cr（NPN）Cl 2.23 Me 0.77 ]（2），而与AlMe 3在甲苯中的反应导致部分卤化物的提取并产生了双核，氯化物桥联的双金属配合物[ fac -Cr（NPN）Me（μ-Cl）} 2 ] [AlMe x Cl4– x ] 2（3 ·[AlMe x Cl 4– x ] 2），其中金属中心由两个氯化物配体桥接。从1与AlEt 3的反应中以高收率分离出复杂的fac- [Cr（NPN）Cl 2 Et]（4），其中含有Cr III -Et功能的罕见实例。用EtAlCl 2处理1后，双核Cr（III）络合物[ fac- Cr（NPN）}
• Bis(arylimino)pyridine derivatives of Group 4 metals: preparation, characterization and activity in ethylene polymerization
  作者：Fausto Calderazzo、Ulli Englert、Guido Pampaloni、Roberto Santi、Anna Sommazzi、Marianna ZinnaPresent address: Polimeri Euro

  DOI：10.1039/b415997g

  日期：——

  Titanium tetrachloride reacts with 2,6-bis[(1-phenylimino)ethyl]pyridine, 1, and 2,6-bis[1-(2,6-diisopropylphenylimino)ethyl]pyridine, 2, giving the adducts of general formulae [Ti(1)Cl3]Cl, 3, and [Ti(2)Cl3]Cl, 6, the latter through the intermediacy of the covalently bonded [Ti(2)Cl4], 4. Heating 6 leads to reduction to the titanium(III) derivative [Ti(2)Cl3], 12, the latter characterized by X-ray

  四氯化钛与2,6-双[（1-苯基亚氨基）乙基]吡啶1反应，然后2,6-双[1-（2,6-二异丙基苯基亚氨基）乙基]吡啶，2给出通式[Ti（1）Cl 3 ] Cl，3和[Ti（2）Cl 3 ] Cl，6的加合物，后者是通过共价键合的[Ti（2）Cl 4的中间体）]，4。加热6导致减少生成钛（III）衍生物[Ti（2）Cl 3 ]，12，后者的特征是X射线衍射方法。[Ti（1）Cl 3 ] Cl与氢的反应甲苯 MAO的解决方案继续进行 甲基化在邻位的-位吡啶环得到钛（IV）衍生物[Ti（C 22 H 21 N 3）Cl 3 ]，8。[Ti（2）Cl 3 ] Cl与MAO的反应产生了包含[Ti（2）Cl 2（OAlCl 3）]，9的产物混合物。单晶X射线衍射研究表明，通过将6与AlOCl反应独立制备的化合物9是包含–OAlCl 3部分的化合物的罕见情况。来自锆和ha的四氯化物，含1或2，已经以高收率获得了相应的加合物[M（L）Cl
• Active Intermediates in Ethylene Polymerization over Titanium Bis(phenoxyimine) Catalysts
  作者：Konstantin P. Bryliakov、Evgenii A. Kravtsov、Dale A. Pennington、Simon J. Lancaster、Manfred Bochmann、Hans H. Brintzinger、Evgenii P. Talsi

  DOI：10.1021/om0505920

  日期：2005.11.1

  in living olefin polymerization over homogeneous catalysts based on bis[N-(3-tert-butylsalicylidene)-2,3,4,5,6-pentafluoroanilinato]titanium(IV) dichloride (L2TiCl2) have been studied. Outer sphere ion pairs [L2TiMe(S)]+[Me-MAO]- and [L2TiMe(S)]+[B(C6F5)4]- (S = solvent molecule), formed by activation of L2TiCl2 with MAO or with AlMe3/[CPh3]+[B(C6F5)4]-, and reactions of these ion pairs with ethene

  研究了基于二氯化双[ N-（3-叔丁基水杨基）-2,3,4,5,6-五氟苯胺基]钛（IV）（L 2 TiCl 2）的均相催化剂上活性烯烃聚合反应中的反应中间体。通过激活形成的外球离子对[L 2 TiMe（S）] + [Me-MAO] -和[L 2 TiMe（S）] + [B（C 6 F 5）4 ] -（S =溶剂分子） L的2的TiCl 2与MAO或ALME 3 / [器CPh 3 ] + [B（C6 F 5）4 ] -，以及这些离子对与乙烯的反应，以提供链增长物质[L 2 TiP] + [Me-MAO] -和[L 2 TiP] + [B（C 6 F 5）4 ] -（P =增长的聚合基链）已通过1 H，13 C和19 F NMR光谱表征。