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Vanadium(v) tetra-phenolate complexes: synthesis, structural studies and ethylene homo-(co-) polymerization capability

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posted on 25.01.2016, 12:25 by Carl Redshaw, Mark J. Walton, Mark ElsegoodMark Elsegood, Timothy J. Prior, Kenji Michiue
Reaction of the ligand α,α,α′,α′-tetrakis(3,5-di-tert-butyl-2-hydroxyphenyl)-p-xylene (p-L1H4) with two equivalents of [VO(OR)3] (R = nPr, tBu) in refluxing toluene afforded, after work-up, the complexes {[VO(OnPr)(THF)]2(-p-L1)}·2(THF) (1·2(THF)) or {[VO(OtBu)]2(-p-L1)}·2MeCN (2·2MeCN), respectively in moderate to good yield. A similar reaction using the meta ligand, namely α,α,α′,α′-tetrakis(3,5-di-tert-butyl-2-hydroxyphenyl)-m-xylene (m-L2H4) afforded the complex {[VO(OnPr)(THF)]2(-p-L2)} (3). Use of [V(Np-R1C6H4)(tBuO)3] (R1 = Me, CF3) with p-L1H4 led to the isolation of the oxo-imido complexes {[VO(tBuO)][V(Np-R1C6H4)(tBuO)](-p-L1)} (R1 = Me, 4·CH2Cl2; CF3, 5·CH2Cl2), whereas use of [V(Np-R1C6H4)Cl3] (R1 = Me, CF3) in combination with Et3N/p-L1H4 or p-L1Na4 afforded the diimido complexes {[V(Np-MeC6H4)(THF)Cl]2(-p-L1)}·4toluene (6·4toluene) or {[V(Np-CF3C6H4)(THF)Cl]2(-p-L1)} (7). For comparative studies, the complex [(VO)(μ-OnPr)L3]2 (8) has also been prepared via the interaction of [VO(nPrO)3] and 2-(α-(2-hydroxy-3,5-di-tert-butylphenyl)benzyl)-4,6-di-tert-butylphenol (L3H2). The crystal structures of 1·2THF, 2·2MeCN, 3, 4·CH2Cl2, 5·CH2Cl2, 6·4toluene·thf, 7 and 8 have been determined. Complexes 1 – 3 and 5 - 8 have been screened as pre-catalysts for the polymerization of ethylene in the presence of a variety of co-catalysts (with and without a re-activator), including DMAC (dimethylaluminium chloride), DEAC (diethylaluminium chloride), EADC (ethylaluminium dichloride) and EASC (ethylaluminium sesquichloride) at various temperatures and for the co-polymerization of ethylene with propylene; results are compared versus the benchmark catalyst [VO(OEt)Cl2]. In some cases, activities as high as 243,400 g/mmolV.h (30.43 Kg PE/mmolV.h.bar) were achievable, whilst it also proved possible to obtain higher molecular weight polymers (in comparable yields to the use of [VO(OEt)Cl2]). In all cases with dimethylaluminium chloride (DMAC)/ethyltrichloroacetate (ETA) activation, the activities achieved surpassed those of the benchmark catalyst. In the case of the co-polymerization of ethylene with propylene, Complexes 1 – 3 and 5 - 8 showed comparable or higher molecular weight than [VO(OEt)Cl2] with comparable catalytic activities or higher in the case of the imido complexes 6 and 7.



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RSC Advances






89783 - 89796 (14)


REDSHAW, C. ...et al., 2015. Vanadium(v) tetra-phenolate complexes: synthesis, structural studies and ethylene homo-(co-) polymerization capability. RSC Advances, 5(109), pp. 89783-89796.


© The Authors. Published by the Royal Society of Chemistry.


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This work is made available according to the conditions of the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0) licence. Full details of this licence are available at: https://creativecommons.org/licenses/by-nc-nd/4.0/

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This paper was accepted for publication in the journal RSC Advances and the definitive published version is available at http://dx.doi.org/10.1039/c5ra20177b