Highly active, thermally stable, ethylene-polymerisation pre-catalysts based on niobium/tantalum-imine systems

Carl Redshaw, Mark Walton, Lucy Clowes, David L. Hughes, Anne-Marie Fuller, Yimin Chao, Alex Walton, Victor Sumerin, Pertti Elo, Igor Soshnikov, Weizhen Zhao, Wen-Hua Sun

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24 Citations (Scopus)


The reactions of MCl or MOCl with imidazole-based pro-ligand LH, 3,5-tBu-2-OH-CH -(4,5-Ph-1H-)imidazole, or oxazole-based ligand L H, 3,5-tBu-2-OH-CH(1H- phenanthro[9,10-d])oxazole, following work-up, afforded octahedral complexes [MX(L)], where MX=NbCl (L, 1 a; L , 2 a), [NbOCl(NCMe)] (L, 1 b; L , 2 b), TaCl (L, 1 c; L, 2 c), or [TaOCl(NCMe)] (L, 1 d). The treatment of α-diimine ligand L, (2,6-iPrCH N=CH), with [MCl(thf)] (M=Nb, Ta) afforded [MCl(L)] (M=Nb, 3 a; Ta, 3 b). The reaction of [MCl(dme)] (dme=1,2-dimethoxyethane; M=Nb, Ta) with bis(imino)pyridine ligand L, 2,6-[2,6-iPrC HN=(Me)C]CHN, afforded known complexes of the type [MCl(L)] (M=Nb, 4 a; Ta, 4 b), whereas the reaction of 2-acetyl-6-iminopyridine ligand L , 2-[2,6-iPrCHN=(Me)C]-6-Ac- CHN, with the niobium precursor afforded the coupled product [({2-Ac-6-(2,6-iPrCHN=(Me)C)C HN}NbOCl)] (5). The reaction of MCl with Schiff-base pro-ligands LH-LH, 3,5-(R)-2-OH-CHCH=N(2-OR -CH), (LH: R=tBu, R=Ph; LH: R=tBu, R=Me; L H: R=Cl, R=Ph; LH: R =Cl, R=Me; LH: R=Cl, R =CF) afforded [MCl(L)] complexes (M=Nb, 6 a-10 a; M=Ta, 6 b-9 b). In the case of compound 8 b, the corresponding zwitterion was also synthesised, namely [TaCl (LH)]×MeCN (8 c). Unexpectedly, the reaction of LH with TaCl at reflux in toluene led to the removal of the methyl group and the formation of trichloride 7 c [TaCl (L)]; conducting the reaction at room temperature led to the formation of the expected methoxy compound (7 b). Upon activation with methylaluminoxane (MAO), these complexes displayed poor activities for the homogeneous polymerisation of ethylene. However, the use of chloroalkylaluminium reagents, such as dimethylaluminium chloride (DMAC) and methylaluminium dichloride (MADC), as co-catalysts in the presence of the reactivator ethyl trichloroacetate (ETA) generated thermally stable catalysts with, in the case of niobium, catalytic activities that were two orders of magnitude higher than those previously observed. The effects of steric hindrance and electronic configuration on the polymerisation activity of these tantalum and niobium pre-catalysts were investigated. Spectroscopic studies (H NMR, C NMR and H-H and H- C correlations) on the reactions of compounds 4 a/4 b with either MAO(50) or AlMe/[CPh][B(CF )] were consistent with the formation of a diamagnetic cation of the form [LAlMe] (MAO(50) is the product of the vacuum distillation of commercial MAO at +50 °C and contains only 1 mol % of Al in the form of free AlMe). In the presence of MAO, this cationic aluminium complex was not capable of initiating the ROMP (ring opening metathesis polymerisation) of norbornene, whereas the 4 a/4 b systems with MAO(50) were active. A parallel pressure reactor (PPR)-based homogeneous polymerisation screening by using pre-catalysts 1 b, 1 c, 2 a, 3 a and 6 a, in combination with MAO, revealed only moderate-to-good activities for the homo-polymerisation of ethylene and the co-polymerisation of ethylene/1-hexene. The molecular structures are reported for complexes 1 a-1 c, 2 b, 5, 6 a, 6 b, 7 a, 8 a and 8 c. Ta very much: The combination of a niobium or tantalum pre-catalyst that contains an imine-based ligand set and a MeAlCl (MADC) co-catalyst is capable, in the presence of ethyl trichloroacetate (ETA), of polymerising ethylene with activities in excess of 11 000 g mmol h bar for niobium and 20 000 g mmol h bar for tantalum. These systems produced essentially linear, high-molecular-weight polyethylene.
Original languageEnglish
Pages (from-to)8884-8899
Number of pages16
JournalChemistry - A European Journal
Issue number27
Publication statusPublished - 1 Jul 2013

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