(Cp*Al)₄ | 132645-87-5

• 分子结构分类: 有机化合物
• 英文名称: (Cp*Al)₄
• 英文别名: (AlCp*)₄；(Al(pentamethylcyclopentadienyl))₄
• CAS: 132645-87-5
• 化学式: C₄₀H₆₀Al₄
• 分子量: 648.843
• InChiKey: DZNDHSDCNBMNMK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  (Cp*Al)₄ 以 甲苯 为溶剂， 生成 氢化铝
  参考文献：
  名称：

  Aluminum(I) and Gallium(I) Compounds: Syntheses, Structures, and Reactions

  摘要：

  AbstractBy the end of the last century there were already the first indications of the possible existence of Al1 halides. However, it was only through the pioneering works of W. Klemm, who would have celebrated his 100th birthday on January 6, 1996, that detailed spectroscopic investigations became possible. Since the end of the 1970s the reactivity of AlX and GaX species in solid noble gases has been confirmed by numerous examples. In recent years formally monovalent Al and Ga species have been successfully synthesized on a preparative scale. In addition to the first halides, organometallic compounds with metal–metal bonds have been isolated and investigated with regard to their chemical properties. The fundamental importance of such species has been documented in this journal among others in the form of two highlight articles in which experimental and theoretical aspects have been examined with examples, and parallels and differences with respect to boron chemistry have been illustrated. This review is intended to give an account of the chronological development of this research area over the last few years, but an attempt is also made to categorize the experimental results achieved not only with respect to structure, thermodynamics, and reactivity, but also with the aid of quantum chemical calculations and by comparative considerations.

  DOI：

  10.1002/anie.199601291
• 作为产物：
  描述：

  [bis(pentametylcyclopentadienyl)di(μ-iodo)diiododialane(II)] 在 sodium 、 potassium 作用下， 以 甲苯 为溶剂， 以53%的产率得到(Cp*Al)₄
  参考文献：
  名称：

  用于还原单烷基铝（III）化合物的钠钾合金

  摘要：

  的类型的单烷基（III）的化合物[R的Al X 2 { - [R =的Cp *（C 5我5），X =氯，溴，I（1-3）; （BisAlCl 2）2（Bis =（Me 3 Si）2 CH）（5）; TrisSi [（Me 3 Si）3 Si]，X = Cl，Br，I（6-8）；制备了CycTris [（CycMe 2 Si）（Me 3 Si）2 C]，X = Me，F，Cl，Br，I（11-15）}，并通过NMR，IR和质谱进行了表征，以及元素分析。Cp的单晶X射线结构* AlBr 2，TrisSiAl X 2 ·THF（X = Cl，Br，I），CycTrisAl X 2 ·THF（X = Me，Cl，Br，I）和[CycTrisAl（μ- O（CH 2）3 CH 2）]报告了2个。使用Na / K合金还原Cp * Al X 2（X = Cl，Br，I）后，分离出单烷基铝（I）化合物（Cp

  DOI：

  10.1006/jssc.2001.9278

文献信息

• Reactivity of Cp*Al towards Silanols: Formation and Hydrolysis of Alumosiloxanes
  作者：Philipp Wittwer、Adrian Stelzer、Thomas Braun

  DOI：10.1002/ejic.201800564

  日期：2018.7.23

  Treatment of [Cp*Al]4 (1) (Cp* = pentamethylcyclopentadienyl) with various silanols gave access to the compounds [AlOSi(OtBu)3}3(DMAP)] (3) (DMAP = 4‐dimethylaminopyridine), [HNEt3][Al(OSiPh3)4] (4), and [Al7(OH)9(OSiiPr2)2O}6] (6). ESI mass spectrometry revealed that 6 exchanges its outer hydroxyl groups in the presence of H218O water. Hydrolysis of 4 led to the formation of [HNEt3][Al(OH)(OSiPh3)3]

  用各种硅烷醇处理[Cp * Al] 4（1）（Cp * =五甲基环戊二烯基），可以得到化合物[Al OSi（O t Bu）3 } 3（DMAP）]（3）（DMAP = 4-二甲基氨基吡啶），[HNEt 3 ] [Al（OSiPh 3）4 ]（4）和[Al 7（OH）9 （OSi i Pr 2）2 O} 6 ]（6）。ESI质谱显示，在H 2 18存在下6交换了其外部羟基哦，水。4的水解导致[HNEt 3 ] [Al（OH）（OSiPh 3）3 ]（5）的形成，但仅在存在其他NEt 3的情况下。在的固态结构6·甲苯，6·（THF）3，6·（H 2 ö · 2THF）3，和5是由X射线晶体学确定。
• C–F bond activation by pentamethylcyclopentadienyl-aluminium(<scp>i</scp>): a combined experimental/computational exercise
  作者：Oleksandr Kysliak、Helmar Görls、Robert Kretschmer

  DOI：10.1039/d0cc00003e

  日期：——

  The reaction of (Cp*Al)4 with a series of fluoro(hetero)arenes has been investigated and C–F bond activation was observed with perfluorotoluene, pentafluoropyridine as well as 1,2,3,4-tetrafluoro-, pentafluoro- and hexafluorobenzene. The reaction mechanism has been probed by means of DFT calculations and the computational findings are in good agreement with the experimental observations.

  研究了（Cp * Al）4与一系列氟（杂）芳烃的反应，并观察到了全氟甲苯，五氟吡啶以及1,2,3,4-四氟，五氟和三氟吡啶的CF键活化六氟苯。通过DFT计算对反应机理进行了探索，计算结果与实验结果吻合良好。
• “Give me five” – an amino imidazoline-2-imine ligand stabilises the first neutral five-membered cyclic triel(<scp>i</scp>) carbenoides
  作者：Lars Denker、Bartosz Trzaskowski、René Frank

  DOI：10.1039/d1cc00010a

  日期：——

  present the first cyclic five-membered triel(I) carbenoides E(AmIm) for E = Ga, In, Tl; AmIm = amido imidazoline-2-imine, which fill the current gap between four- and six-membered triel(I) carbenoides supported by HGiso and HNacNac. Ga(AmIm) can act as a strong σ-donor ligand in transition metal complexes, while the intermediacy of the Al(I) carbenoide Al(AmIm) is rationalised based on the isolation

  我们提出了第一个环状的五元triel（I）碳烯化物E（AmIm），其中E = Ga，In，Tl；AmIm =酰胺基咪唑啉-2-亚胺，它填补了由HGiso和HNacNac所支持的四元和六元triel（I）碳烯化物之间的当前缺口。在过渡金属配合物中，Ga（AmIm）可以充当强大的σ供体配体，而Al（I）碳烯化物Al（AmIm）的中间体是基于Al（III）插入产物的分离而合理化的。
• Salt metathesis as an alternative approach to access aluminium(<scp>i</scp>) and gallium(<scp>i</scp>) β-diketiminates
  作者：Oleksandr Kysliak、Helmar Görls、Robert Kretschmer

  DOI：10.1039/d0dt01342k

  日期：——

  the respective aluminium(i) and gallium(i) β-diketiminates I and II. The protocol gives better yields compared to the established procedures and avoids the use of strong reducing agents such as metallic potassium. Furthermore, the aluminium(i) β-diketiminate I was found to react with itself and yields upon C-N bond cleavage and hydrogen-atom transfer the asymmetric dinuclear aluminium(iii) complex V

  盐复分解，即β-二酮化钠分别与（AlCp *）4和GaCp *的反应，是获取各自的β-二酮化铝I和II的有价值的途径。与已建立的程序相比，该方案可提供更好的收率，并且避免使用强还原剂，例如金属钾。此外，发现β-二酮铝（i）与自身发生反应，并在CN键断裂和氢原子转移时产生不对称的双核铝（iii）配合物V，其易于通过结晶与I分离。通过DFT和DLPNO-CCSD（T）计算对反应机理进行了探索，计算结果与实验结果吻合良好。
• Reactivity of mono- and divalent aluminium compounds towards group 15 nanoparticles
  作者：Adrian Hauser、Luca Münzfeld、Peter W. Roesky

  DOI：10.1039/d1cc01475g

  日期：——

  Al–Sb compound [(AlCp*)3Sb2]. Additionally, two different dialanes [AlCp*X]2 (X = Br, I) were employed as one-electron reducing agents, forming calix like coordination compounds upon reaction with nano arsenic. The isolated species significantly enlarge the accessible structural variety of molecular group 13/15 compounds, highlighting the exceptional utility and reactivity of nanoscale group 15 precursors

  在这里，我们提出了一种新的方法来处理有机金属13/15族化合物，即纳米颗粒砷和锑与低价铝物质的反应。双电子还原剂[AlCp *] 4（Cp * = C 5 Me 5）与砷纳米颗粒的反应产生了两个前所未有的十和十二烷Al-As簇的混合物。相反，纳米锑的类似转化产生了已知的Al-Sb化合物[（AlCp *）3 Sb 2 ]。另外，两种不同的二烷[AlCp * X] 2（X = Br，I）被用作单电子还原剂，形成杯与纳米砷反应后的配位化合物。分离出的物种显着扩大了分子组13/15化合物的可及结构多样性，突出了纳米级15组前体的特殊用途和反应活性。