Vanadium Olefin Polymerization Catalysts: NMR Spectroscopic Characterization of V(III) Intermediates | Sciact - CRIS-system of Boreskov Institute of Catalysis

Vanadium Olefin Polymerization Catalysts: NMR Spectroscopic Characterization of V(III) Intermediates Full article

Journal

Journal of Organometallic Chemistry
ISSN: 0022-328X

Output data

Year: 2018, Volume: 867, Pages: 4-13 Pages count : 10 DOI: 10.1016/j.jorganchem.2017.08.020

Tags

Active species, Bis(imino)pyridine, Ethylene polymerization, NMR, Vanadium, α-diimine

Authors

Soshnikov Igor E. ^1,2 , Semikolenova Nina V. ¹ , Bryliakov Konstantin P. ^1,2 , Zakharov Vladimir A. ^1,2 , Talsi Evgenii P. ^1,2

Affiliations

1	Federal Agency for Scientific Organizations, Siberian Branch of the Russian Academy of Sciences, Boreskov Institute of Catalysis, 630090, Novosibirsk, Pr. Lavrentieva, 5, Russian Federation
2	The Ministry of Education and Science of the Russian Federation, Novosibirsk State University, 630090, Novosibirsk, Pirogova Street, 2, Russian Federation

Funding (2)

1	Russian Foundation for Basic Research	16-03-00236
2	Federal Agency for Scientific Organizations	0303-2016-0009

Vanadium(III) species formed upon reacting α-diimine (1) and bis(imino)pyridine (5) vananadium(III) pre-catalysts with MAO, AlMe2Cl, AlMe2Cl/[Ph3C][B(C6F5)4], and AlMe3/[Ph3C][B(C6F5)4] have been characterized in detail by 1H, 2H, and 19F NMR spectroscopy; the VIII-CH3 moiety has been observed by 1H and 2H NMR spectroscopy. For complex 1, zwitterion-like species [L′VIIIR2+···MeMAO−] and ion pairs [L′VIIIR2(THF)2]+[A]- (L′ = 1,4-bis-3,5-dimethylphenyl-2,3-dimethyl-1,4-diazabuta-1,3-diene; [A]− = [MeMAO]− or [B(C6F5)4]−) have been identified. The outer-sphere ion pairs of the type [L(Cl)VIII(μ-Cl)2AlMe2]+[A]−, [L(Me)VIII(μ-Cl)2AlMe2]+[A]−, [LVIIICl2(THF)]+[A]− and [LVIII(Cl)Me(THF)]+[A]− (L = 2,6-bis[1-(2,6-dimethylphenylimino)ethyl]pyridine; [A]− = [AlMe3Cl]− or [B(C6F5)4]−) have been found in the systems based on the complex 5. The nature of the vanadium species active in ethylene polymerization and the catalyst deactivation pathways are discussed.

Soshnikov I.E. , Semikolenova N.V. , Bryliakov K.P. , Zakharov V.A. , Talsi E.P.
Vanadium Olefin Polymerization Catalysts: NMR Spectroscopic Characterization of V(III) Intermediates
Journal of Organometallic Chemistry. 2018. V.867. P.4-13. DOI: 10.1016/j.jorganchem.2017.08.020 WOS Scopus РИНЦ ANCAN OpenAlex

Submitted:	Aug 11, 2017
Accepted:	Aug 31, 2017
Published online:	Sep 6, 2017
Published print:	Jul 15, 2018

Web of science:	WOS:000433256800003
Scopus:	2-s2.0-85029667374
Elibrary:	35514820
Chemical Abstracts:	2017:1541483
Chemical Abstracts (print):	168:502949
OpenAlex:	W2753102503

DB	Citing
Web of science	11
Scopus	11
OpenAlex	12