EPR Monitoring of Vanadium(IV) Species Formed upon Activation of Vanadium(V) Polyphenolate Precatalysts with AlR2Cl and AlR2Cl/Ethyltrichloroacetate (R = Me, Et) | Sciact - CRIS-system of Boreskov Institute of Catalysis

EPR Monitoring of Vanadium(IV) Species Formed upon Activation of Vanadium(V) Polyphenolate Precatalysts with AlR2Cl and AlR2Cl/Ethyltrichloroacetate (R = Me, Et) Full article

Journal

Organometallics
ISSN: 0276-7333 , E-ISSN: 1520-6041

Output data

Year: 2009, Volume: 28, Number: 23, Pages: 6714-6720 Pages count : 7 DOI: 10.1021/om900515h

Tags

OLEFIN POLYMERIZATION CATALYST; CAPPED TRIS(PHENOLATE) COMPLEXES; ETHYLENE POLYMERIZATION; THERMALLY ROBUST; SINGLE-SITE; LIGANDS; PROCATALYSTS; HOMOPOLYMERIZATION; COPOLYMERIZATION; ALUMINUM

Authors

Soshnikov Igor E. ^1,2 , Semikolenova Nina V. ¹ , Shubin Alexander A. ^1,2 , Brylyakov Konstantin P. ^1,2 , Zakharov Vladimir A. ¹ , Redshaw Carl ³ , Talzi Evgenii P. ^1,2

Affiliations

1	Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, 630090, Novosibirsk, Russian Federation
2	Novosibirsk State University, 630090, Novosibirsk, Russian Federation
3	School of Chemistry, University of East Anglia, Norwich NR4 7TJ, U.K.

Funding (1)

Russian Foundation for Basic Research

09-03-00485

Reactions of the vanadyl polyphenolate complexes {VO[p-tert-butylcalix[4]arene(O)3(OMe)]} (1) and [VO(OArCH2Ar′CH2OAr)]2 (Ar = 4,6-tert-butylphenol; Ar′ = 4-tert-butylphenol) (2) with AlR3 and AlR2Cl, in the absence and in the presence of reactivator (ethyltrichloroacetate, ETA), were monitored by EPR (R = Me, Et). It was shown, that vanadium(IV) complexes with proposed structures L1VIVR(AlR3) and L1VIVR(AlR2Cl) are formed upon interaction of 1 with AlR3 and AlR2Cl, respectively (20 °C, L1 is the initial oxo-calix[4]arene ligand). Similarly, vanadium(IV) complexes with proposed structures L2VIVR(AlR3) and L2VIVR(AlR2Cl) are formed upon interaction of 2 with AlR3 and AlR2Cl (L2 is the initial ligand of 2). The growth of the concentration of L1VIVR(AlR2Cl) and L2VIVR(AlR2Cl) correlates with the increase of the ethylene polymerization activity of the catalyst systems 1,2/AlR2Cl/ETA. It is proposed therefore that vanadium(IV) species of the type L1VIVR(AlR2Cl) and L2VIVR(AlR2Cl) can be the active species (or their immediate precursors) of the catalyst system 1,2/AlR2Cl/ETA.

Soshnikov I.E. , Semikolenova N.V. , Shubin A.A. , Brylyakov K.P. , Zakharov V.A. , Redshaw C. , Talzi E.P.
EPR Monitoring of Vanadium(IV) Species Formed upon Activation of Vanadium(V) Polyphenolate Precatalysts with AlR2Cl and AlR2Cl/Ethyltrichloroacetate (R = Me, Et)
Organometallics. 2009. V.28. N23. P.6714-6720. DOI: 10.1021/om900515h WOS Scopus РИНЦ ANCAN OpenAlex

Submitted:	Jun 17, 2009
Published online:	Nov 11, 2009
Published print:	Dec 14, 2009

Web of science:	WOS:000272560700017
Scopus:	2-s2.0-71949092481
Elibrary:	15307033
Chemical Abstracts:	2009:1399864
Chemical Abstracts (print):	152:65785
OpenAlex:	W1985863077

DB	Citing
Web of science	40
Scopus	43
OpenAlex	46