Liquid metal alkyls are strong Lewis acids and bases and useful solvents in which to conduct organometallic reactions. Cp2ZrMe2 undergoes rapid methyl exchange with pure Me3Al but reacts with EtAlMe2 in Me3Al to form Cp2Zr(mu-CH3)(mu-CH2CH2)AlMe2. Neat R3Al reagents in which R has a hydrogen atom produce solvated Cp2ZrH2 derivatives. The gas-phase reaction of Cp2ZrCH3+ with Me3Al, studied by ion cyclotron resonance spectrometry, produces an ion formulated as Cp2Zr(mu-CH2)2Al+.
Solvolysis of dimethylzirconocene by trialkylaluminum compounds
作者:A. R. Siedle、R. A. Newmark、J. N. Schroepfer、P. A. Lyon
DOI:10.1021/om00048a013
日期:1991.2
Liquid metal alkyls are strong Lewis acids and bases and useful solvents in which to conduct organometallic reactions. Cp2ZrMe2 undergoes rapid methyl exchange with pure Me3Al but reacts with EtAlMe2 in Me3Al to form Cp2Zr(mu-CH3)(mu-CH2CH2)AlMe2. Neat R3Al reagents in which R has a hydrogen atom produce solvated Cp2ZrH2 derivatives. The gas-phase reaction of Cp2ZrCH3+ with Me3Al, studied by ion cyclotron resonance spectrometry, produces an ion formulated as Cp2Zr(mu-CH2)2Al+.
Zirconium-Catalyzed C–H Alumination of Polyolefins, Paraffins, and Methane
作者:Uddhav Kanbur、Alexander L. Paterson、Jessica Rodriguez、Andrew L. Kocen、Ryan Yappert、Ryan A. Hackler、Yi-Yu Wang、Baron Peters、Massimiliano Delferro、Anne M. LaPointe、Geoffrey W. Coates、Frédéric A. Perras、Aaron D. Sadow
DOI:10.1021/jacs.2c11056
日期:2023.2.8
C–H/Et-Al exchange in zirconium-catalyzed reactions of saturated hydrocarbons and AlEt3 affords versatile organoaluminum compounds and ethane. The grafting of commercially available Zr(OtBu)4 on silica/alumina gives monopodal ≡SiO–Zr(OtBu)3 surface pre-catalyst sites that are activated in situ by ligand exchange with AlEt3. The catalytic C–H alumination of dodecane at 150 °C followed by quenching in
锆催化的饱和烃和 AlEt 3反应中的 C–H/Et-Al 交换提供了多种有机铝化合物和乙烷。将市售 Zr(O t Bu) 4接枝到二氧化硅/氧化铝上,得到单足 ≡SiO–Zr(O t Bu) 3表面预催化剂位点,这些位点通过与 AlEt 3的配体交换原位激活。十二烷在 150 °C 下催化 C-H 铝化,然后在空气中淬火,得到正十二烷醇作为主要产物,显示出甲基活化的选择性。在这些条件下未检测到较短的碳氢化合物或酒精产品。环辛烷与AlEt 3的催化反应然而,提供开环产物,表明 C-C 键断裂很容易在无甲基的反应物中发生。这种对甲基铝化的选择性使得聚乙烯、聚丙烯、聚苯乙烯和聚α-烯烃油的 C-H 铝化反应不会发生明显的链解构。此外,最小的碳氢化合物甲烷在无溶剂催化条件下进行选择性单铝化,为 Al-Me 物种提供了直接途径。