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

Michiue, K.; Redshaw, Carl; Walton, Mark J.; Elsegood, Mark R. J.; Prior, Timothy J.; Michiue, Kenji


K. Michiue

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Professor Carl Redshaw
Professor of Inorganic Materials Chemistry and REF Lead for Chemistry

Mark J. Walton

Mark R. J. Elsegood

Kenji Michiue


Reaction of 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 (μ-p-L¹)}·2(THF) (1·2(THF)) or {[VO(OtBu)]₂ (μ-p-L¹)}·2MeCN (2·2MeCN), respectively in moderate to good yield. A similar reaction using the meta pro-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 (μ-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)](μ-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 (μ-p-L¹)}·4toluene (6·4toluene) or {[V(Np-CF₃C₆H₄)(THF)Cl]₂ (μ-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 mmol⁻¹ V⁻¹ h⁻¹ (30.43 kgPE mmol V⁻¹ h⁻¹ bar⁻¹) 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.

Journal Article Type Article
Publication Date Oct 8, 2015
Journal RSC advances
Print ISSN 2046-2069
Electronic ISSN 2046-2069
Publisher Royal Society of Chemistry
Peer Reviewed Peer Reviewed
Volume 5
Issue 109
Pages 89783-89796
APA6 Citation Redshaw, C., Walton, M. J., Elsegood, M. R. J., Prior, T. J., & Michiue, K. (2015). Vanadium(V) tetra-phenolate complexes: synthesis, structural studies and ethylene homo-(co-)polymerization capability. RSC advances, 5(109), 89783-89796.
Keywords Vanadium, Tetra-phenolate, Polyethylene, Ethylene/propylene copolymer, Crystal structures
Publisher URL!divAbstract
Copyright Statement ©2016 University of Hull
Additional Information Authors' accepted manuscript of article published in: RSC advances, 2015, v.5, issue 109.


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