EPR monitoring of vanadium(IV) species formed upon activation of vanadium(V) polyphenolate precatalysts with AlR2Cl and AlR2Cl/ethyltrichloroacetate (R = Me, Et)

Igor E. Soshnikov; Nina V. Semikolenova; Alexander A. Shubin; Konstantin P. Bryliakov; Vladimir A. Zakharov; Carl Redshaw; Evgenii P. Talsi

doi:10.1021/om900515h

EPR monitoring of vanadium(IV) species formed upon activation of vanadium(V) polyphenolate precatalysts with AlR2Cl and AlR2Cl/ethyltrichloroacetate (R = Me, Et)

Igor E. Soshnikov, Nina V. Semikolenova, Alexander A. Shubin, Konstantin P. Bryliakov, Vladimir A. Zakharov, Carl Redshaw, Evgenii P. Talsi

School of Chemistry

Research output: Contribution to journal › Article › peer-review

41 Citations (Scopus)

Abstract

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 L₁V^IVR(AlR₃) and L₁V^IVR(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 L₂V^IVR(AlR₃) and L₂V^IVR(AlR₂Cl) are formed upon interaction of 2 with AlR₃ and AlR₂Cl (L₂ is the initial ligand of 2). The growth of the concentration of L₁V^IVR(AlR₂Cl) and L₂V^IVR(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 L₁V^IVR(AlR₂Cl) and L₂V^IVR(AlR₂Cl) can be the active species (or their immediate precursors) of the catalyst system 1,2/AlR₂Cl/ETA.

Original language	English
Pages (from-to)	6714-6720
Number of pages	7
Journal	Organometallics
Volume	28
Issue number	23
Early online date	11 Nov 2009
DOIs	https://doi.org/10.1021/om900515h
Publication status	Published - 2009

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10.1021/om900515h

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Soshnikov, Igor E. ; Semikolenova, Nina V. ; Shubin, Alexander A. ; Bryliakov, Konstantin P. ; Zakharov, Vladimir A. ; Redshaw, Carl ; Talsi, Evgenii P. / EPR monitoring of vanadium(IV) species formed upon activation of vanadium(V) polyphenolate precatalysts with AlR2Cl and AlR2Cl/ethyltrichloroacetate (R = Me, Et). In: Organometallics. 2009 ; Vol. 28, No. 23. pp. 6714-6720.

@article{2804184ce692469fb7ff7179d2219a0c,

title = "EPR monitoring of vanadium(IV) species formed upon activation of vanadium(V) polyphenolate precatalysts with AlR2Cl and AlR2Cl/ethyltrichloroacetate (R = Me, Et)",

abstract = "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.",

author = "Soshnikov, {Igor E.} and Semikolenova, {Nina V.} and Shubin, {Alexander A.} and Bryliakov, {Konstantin P.} and Zakharov, {Vladimir A.} and Carl Redshaw and Talsi, {Evgenii P.}",

year = "2009",

doi = "10.1021/om900515h",

language = "English",

volume = "28",

pages = "6714--6720",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "23",

}

EPR monitoring of vanadium(IV) species formed upon activation of vanadium(V) polyphenolate precatalysts with AlR2Cl and AlR2Cl/ethyltrichloroacetate (R = Me, Et). / Soshnikov, Igor E.; Semikolenova, Nina V.; Shubin, Alexander A.; Bryliakov, Konstantin P.; Zakharov, Vladimir A.; Redshaw, Carl; Talsi, Evgenii P.

In: Organometallics, Vol. 28, No. 23, 2009, p. 6714-6720.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - EPR monitoring of vanadium(IV) species formed upon activation of vanadium(V) polyphenolate precatalysts with AlR2Cl and AlR2Cl/ethyltrichloroacetate (R = Me, Et)

AU - Soshnikov, Igor E.

AU - Semikolenova, Nina V.

AU - Shubin, Alexander A.

AU - Bryliakov, Konstantin P.

AU - Zakharov, Vladimir A.

AU - Redshaw, Carl

AU - Talsi, Evgenii P.

PY - 2009

Y1 - 2009

N2 - 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.

AB - 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.

U2 - 10.1021/om900515h

DO - 10.1021/om900515h

M3 - Article

VL - 28

SP - 6714

EP - 6720

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 23

ER -