Abstract
1-Hexene transformations in the catalytic systems L2MCl2–XAlBui2 (L = Cp, M = Ti, Zr, Hf; L = Ind, rac-H4C2[THInd]2, M = Zr; X = H, Bu i) and [Cp2ZrH2]2-ClAlR2 activated by MMAO-12, B(C6F5)3, or (Ph3C)[B(C6F5)4] in chlorinated solvents (CH2Cl2, CHCl3, o-Cl2C6H4, ClCH2CH2Cl) were studied. The systems [Cp2ZrH2]2-MMAO-12, [Cp2ZrH2]2-ClAlBui2-MMAO-12, or Cp2ZrCl2-HAlBui2-MMAO-12 (B(C6F5)3) in CH2Cl2 showed the highest activity and selectivity towards the formation of vinylidene head-to-tail alkene dimers. The use of chloroform as a solvent provides further in situ dimer dimerization to give a tetramer yield of up to 89%. A study of the reaction of [Cp2ZrH2]2 or Cp2ZrCl2 with organoaluminum compounds and MMAO-12 by NMR spectroscopy confirmed the formation of Zr,Zr-hydride clusters as key intermediates of the alkene dimerization. The probable structure of the Zr,Zr-hydride clusters and ways of their generation in the catalytic systems were analyzed using a quantum chemical approach (DFT).
Highlights
Catalytic Systems Activated by MMAO-12, B(C6 F5 )3, or (Ph3 C)[B(C6 F5 )4 ]
The conditions for the selective synthesis of vinylidene dimers in the presence of Catalytic Systems Activated by MMAO-12, B(C6Fi5)3, or (Ph3C)[B(C
As a result of studying the catalytic transformations of 1-hexene under the action of Ti group metallocenes, organoaluminum compounds, and activators MMAO-12, B(C6 F5 )3 or (Ph3 C)[B(C6 F5 )4 ] in chlorinated solvents, it was found that systems based on Zr complexes
Summary
The systems [Cp2 ZrH2 ]2 -MMAO-12, [Cp2 ZrH2 ]2 -ClAlBui 2 -MMAO-12, or Cp2 ZrCl2 HAlBui 2 -MMAO-12 (B(C6 F5 )3 ) in CH2 Cl2 showed the highest activity and selectivity towards the formation of vinylidene head-to-tail alkene dimers. A study of the reaction of [Cp2 ZrH2 ]2 or Cp2 ZrCl2 with organoaluminum compounds and MMAO-12 by NMR spectroscopy confirmed the formation of Zr,Zr-hydride clusters as key intermediates of the alkene dimerization. Alkene dimers and oligomers represent a large class of compounds that are used as comonomers in ethylene polymerization and as raw materials for the production of adhesives, surfactants, fragrances, synthetic lubricating fuel additives, etc. Some research groups are developing strategies for the production of highly efficient jet and diesel fuels via oligomerization of alkenes (1-butene, 1-hexene) synthesized from renewable plant raw materials [2,8]. Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations
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