Sciact
  • EN
  • RU

Vanadium Complexes Derived from Oxacalix[6]arenes: Structural Studies and Use in the Ring Opening Homo-/co-polymerization of ε-Caprolactone/δ-Valerolactone and Ethylene Polymerization Full article

Journal Catalysis Science and Technology
ISSN: 2044-4753 , E-ISSN: 2044-4761
Output data Year: 2021, Volume: 11, Number: 2, Pages: 624-636 Pages count : 13 DOI: 10.1039/D0CY01979H
Tags Aliphatic compounds; Aromatic hydrocarbons; Chlorine compounds; Ethylene; Metal complexes; Vanadium compounds
Authors Xing Tian 1 , Prior Timothy J. 1 , Elsegood Mark R.J. 2 , Semikolenova Nina V. 3 , Soshnikov Igor E. 3,4 , Bryliakov Konstantin 3,4 , Chen Kai 1,5 , Redshaw Carl 1
Affiliations
1 Plastics Collaboratory, Department of Chemistry, University of Hull, Cottingham Road, Hull, HU6 7RX, UK
2 Chemistry Department, Loughborough University, Loughborough, Leicestershire, LE11 3TU, UK
3 Boreskov Institute of Catalysis, Pr. Lavrentieva 5, Novosibirsk 630090, Russian Federation
4 Novosibirsk State University, Pirogova 1, Novosibirsk 630090, Russian Federation
5 Collaborative Innovation Center of Atmospheric Environment and Equipment Technology, Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control, School of Environmental Science and Engineering, Nanjing University of Information Science & Technology, Nanjing 210044, P. R. China

Funding (3)

1 Federal Agency for Scientific Organizations 0303-2016-0009
2 China Scholarship Council
3 Engineering and Physical Sciences Research Council EP/S025537/1

Abstract: Reaction of Na[VO(tBuO)4] (generated in situ from VOCl3 and NaOtBu) with p-tert-butyltetrahomodioxacalix[6]areneH6 (L1H6) afforded, after work-up (in MeCN), the mixed-metal complex [(VO)2(μ-O)Na2(L1)(MeCN)4]·5(MeCN) (1·5MeCN), whilst the oxo complex {[VO]4L1} (2·6MeCN) was isolated via the use of [VO(OnPr)3]. Reaction of L1H6 with [V(Np-CH3C6H4)(OtBu)3] afforded the complex {[V(Np-CH3C6H4)]2L1} (3·7MeCN·0.5CH2Cl2). Use of similar methodology afforded the imido complexes {[V(Np-RC6H4)]2L1} (R = OMe (4); CF3 (5); Cl (6); F (7)); on one occasion, reaction of [V(Np-CH3C6H4)(OEt)3] with L1H6 afforded the product [VO(L2)]2·4MeCN (8·4MeCN) (L2 = 2-(p-CH3-C6H4NCH)-4-tBu-C6H2O-6-CH2)-4-tBuC6H2OH) in which L1 has been cleaved. For comparative catalytic ring opening polymerization (ROP) studies, the known complexes [VOL3] (L3 = oxacalix[3]arene) (I), [V(Np-CH3-C6H4)L3]2 (II), [Li(MeCN)4][V2(O)2Li(MeCN)(L6H2)2] (L6H6 = p-tert-butylcalix[6]areneH6) (III) and [(VO)2L8H] (L8H8 = p-tert-butylcalix[8]areneH8) (IV) have also been prepared. ROP studies, with or without external alcohol present, indicated that complexes 1 to 8 exhibited moderate to good conversions for ε-Cl, δ-VL and the co-polymerization thereof. Within the imido series, a positive influence was observed when electron withdrawing substituents were present. These systems afforded relatively low molecular weight products and were also inactive toward the ROP of rac-lactide. In the case of ethylene polymerization, complexes 3, 5 and 7 exhibited highest activity when screened in the presence of dimethylaluminium chloride/ethyltrichloroacetate; the activity of 4 was much lower. The products were highly linear polyethylene with Mw in the range 74–120 × 103 Da.
Cite: Xing T. , Prior T.J. , Elsegood M.R.J. , Semikolenova N.V. , Soshnikov I.E. , Bryliakov K. , Chen K. , Redshaw C.
Vanadium Complexes Derived from Oxacalix[6]arenes: Structural Studies and Use in the Ring Opening Homo-/co-polymerization of ε-Caprolactone/δ-Valerolactone and Ethylene Polymerization
Catalysis Science and Technology. 2021. V.11. N2. P.624-636. DOI: 10.1039/D0CY01979H WOS Scopus РИНЦ AN OpenAlex
Files: Full text from publisher
Dates:
Submitted: Oct 10, 2020
Accepted: Nov 19, 2020
Published online: Nov 19, 2020
Published print: Jan 21, 2021
Identifiers:
Web of science: WOS:000613888900020
Scopus: 2-s2.0-85098214745
Elibrary: 45051190
Chemical Abstracts: 2020:2394630
OpenAlex: W3109289680
Citing:
DB Citing
Scopus 11
Web of science 11
Elibrary 10
OpenAlex 9
Altmetrics: