Mmao 12

TIBA (1 M solution in hexane, Merck, NJ, USA), MMAO-12 (1.52 M solution in Toluene, Merck, NJ, USA), azobisisobutyronitrile (AIBN, Merck, NJ, USA), benzoyl peroxide (Merck, NJ, USA), mesitylene (Merck, NJ, USA) and CDCl₃ (99.8% ²H, Cambridge Isotope Laboratories, Inc., MS, USA) were used as purchased. Toluene (Merck, NJ, USA) was refluxed over sodium and stored under argon atmosphere. Maleic anhydride (MA, Merck, NJ, USA) was recrystallized from Toluene before use. Hex-1-ene (Merck, NJ, USA) was stored over Na wire and distilled under argon. The ¹H NMR spectra were recorded on a Bruker AVANCE 400 spectrometer (400 MHz, Bruker, MS, USA) at 20 °C. The chemical shifts are reported in ppm relative to the solvent residual peaks.
Zirconium complex 1 was prepared in accordance with published procedure [81 (link)]. Dimerization of hex-1-ene was conducted in liquid olefin media in the presence of 1, activated by TIBA and MMAO-12 using the protocol described previously [47 (link),49 (link)], 5-methyleneundecane was separated by the vacuum distillation, b. p. 80 °C at 7 Torr.

All operations for organometallic compounds were performed under argon according to the Schlenk technique. The zirconocene dichloride was prepared using the standard procedure from ZrCl₄ (99.5%, Merck, Darmstadt, Germany) [65 ]. The synthesis of [Cp₂ZrH₂]₂ from Cp₂ZrCl₂ was performed as described previously [29 (link),30 (link),31 (link)]. The solvents (benzene, toluene) were distilled from AlBuⁱ₃ immediately before use. Commercially available HAlBuⁱ₂ (99%, Merck, Darmstadt, Germany), ClAlEt₂ (97%, Strem, Kehl, Germany), AlBuⁱ₃ (95%, Strem, Kehl, Germany), AlEt₃ (98%, Merck, Darmstadt, Germany), AlMe₃ (97%, Merck, Darmstadt, Germany) MMAO-12 (7% Al in toluene, Merck, Darmstadt, Germany) were involved into the reactions. CAUTION: the pyrophoric nature of aluminum alkyl and hydride compounds require special safety precautions in their handling. Terminal alkenes 1-hexene (97%, Acros, Geel, Belgium), 1-octene (99%, Acros, Geel, Belgium), 1-decene (95%, Acros, Geel, Belgium), 4-methyl-1-pentene (97%, Acros, Geel, Belgium), allylbenzene (98%, Acros, Geel, Belgium), styrene (99%, Fisher, Hampton, NH, USA) were used as received. NMR data, mass spectra of the obtained dimers 4a–f correspond to the data, presented in Refs. [5 (link),10 (link),11 (link),66 (link)].

TIBA (1 M solution in hexane, Merck, Darmstadt, Germany), MMAO-12 (1.52 M solution in toluene, Merck), (η⁵-C₅H₅)₂ZrCl₂ (Merck), and CDCl₃ (99.8% ²H, Cambridge Isotope Laboratories, Inc., MS, USA) were used as purchased. 1-Hexene (Merck) was stored over Na wire and distilled under argon. The ¹H NMR spectra were recorded on a Bruker AVANCE 400 spectrometer (400 MHz, Bruker, MS, USA) at 20 °C. The chemical shifts are reported in ppm relative to the solvent residual peaks. The distribution of oligomers produced in zirconocene-catalyzed reactions was measured by gas chromatography (GC) method. GC analysis was carried out with a KRISTALL-2000M gas chromatograph (Meta-chrom Ltd., Yoshkar-Ola, Russian Federation) equipped with a SolGel-1ms (60 m × 0.25 mm × 0.25 μm) column and a flame ionization detector. Helium was used as a carrier gas at a rate of 1.364 cc/min and with a split ratio of 73.3:1. The injection temperature was 320 °C, and the column temperature was 200 °C within 5 min and then increased from 200 °C to 300 °C at a rate of 10 °C/min.