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1-Hexene transformations in the catalytic systems L 2 MCl 2 -XAlBu i  2 (L = Cp, M = Ti, Zr, Hf; L = Ind, rac-H 4 C 2 [THInd] 2 , M = Zr; X = H, Bu i ) and [Cp 2 ZrH 2 ] 2 -ClAlR 2 activated by MMAO-12, B(C 6 F 5 ) 3 , or (Ph 3 C)[B(C 6 F 5 ) 4 ] in chlorinated solvents (CH 2 Cl 2 , CHCl 3 , o-Cl 2 C 6 H 4 , ClCH 2 CH 2 Cl) were studied. The systems [Cp 2 ZrH 2 ] 2 -MMAO-12, [Cp 2 ZrH 2 ] 2 -ClAlBu i  2 -MMAO-12, or Cp 2 ZrCl 2 -HAlBu i  2 -MMAO-12 (B(C 6 F 5 ) 3 ) in CH 2 Cl 2 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 [Cp 2 ZrH 2 ] 2 or Cp 2 ZrCl 2 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).

Ti Group Metallocene-Catalyzed Synthesis of 1-Hexene Dimers and Tetramers