Activation of Bis(phenoxyimino)zirconium Polymerization Catalysts with Methylaluminoxane and AlMe3/[CPh3]+[B(C6F5)4]- | Sciact - CRIS-система Института катализа

Activation of Bis(phenoxyimino)zirconium Polymerization Catalysts with Methylaluminoxane and AlMe3/[CPh3]+[B(C6F5)4]- Научная публикация

Журнал

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

Вых. Данные

Год: 2007, Том: 26, Номер: 19, Страницы: 4810-4815 Страниц : 6 DOI: 10.1021/om7004113

Ключевые слова

Catalyst activity; Nuclear magnetic resonance spectroscopy; Polymerization; Zirconium compounds

Авторы

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

Организации

1	Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, 630090 Novosibirsk, Russian Federation
2	Natural Sciences Department, Novosibirsk State University, 630090 Novosibirsk, Russian Federation

Информация о финансировании (2)

1	Российский фонд фундаментальных исследований	06-03-32700
2	Royal Society	2004/R1-FSU

The intermediates of olefin polymerization over homogeneous catalysts based on bis[N-(3-tert-butylsalicylidene)anilinato]zirconium(IV) dichloride {(LtBu)2ZrCl2} (1-tBu), bis[N-(3-methylsalicylidene)anilinato]zirconium(IV) dichloride {(LMe)2ZrCl2} (1-Me), and bis[N-(salicylidene)anilinato]zirconium(IV) dichloride {(LH)2ZrCl2} (1-H) with different activators {methylaluminoxane (MAO) and AlMe3/[CPh3]+[B(C6F5)4]-} have been studied by 1H and 13C NMR spectroscopy. Heterobinuclear ion pairs [(LtBu)2Zr(μ-Me)2AlMe2]+[Me-MAO]- (2-tBu) and [(LtBu)2Zr(μ-Me)2AlMe2]+[B(C6F5)4]- (2‘-tBu) are formed upon activation of 1-tBu with MAO and AlMe3/[CPh3]+[B(C6F5)4]-, respectively. These species are the precursors of the highly active intermediates of polymerization. In contrast, the activation of 1-Me with MAO results mainly in the formation of the tight ion pair [(LMe)2ZrMe+···Me-MAO-]. This ion pair is the precursor to a poorly active intermediate of polymerization. In the catalytic systems 1-H/MAO and 1-H/AlMe3/[CPh3]+[B(C6F5)4]-, the aluminum ion pairs [LHAl(μ-Me)(μ-Cl)AlMe2]+[Me-MAO]- and [LHAl(μ-Me)(μ-Cl)AlMe2]+[B(C6F5)4]-, which were inactive in ethylene polymerization, are predominantly formed. The isomeric composition of 2‘-tBu is close to that of the initial complex 1-tBu. The main route of the 1-tBu/MAO catalyst deactivation is the ligand transfer to aluminum with the formation of the complex LtBuAlMe2.

Kravtsov E.A. , Bryliakov K.P. , Semikolenova N.V. , Zakharov V.A. , Talsi E.P.
Activation of Bis(phenoxyimino)zirconium Polymerization Catalysts with Methylaluminoxane and AlMe3/[CPh3]+[B(C6F5)4]-
Organometallics. 2007. V.26. N19. P.4810-4815. DOI: 10.1021/om7004113 WOS Scopus РИНЦ CAPlusCA OpenAlex

Поступила в редакцию:	27 апр. 2007 г.
Опубликована online:	8 авг. 2007 г.
Опубликована в печати:	1 сент. 2007 г.

Web of science:	WOS:000249242100019
Scopus:	2-s2.0-34748829738
РИНЦ:	13559333
Chemical Abstracts:	2007:865432
Chemical Abstracts (print):	147:427724
OpenAlex:	W1986164918

БД	Цитирований
Web of science	20
Scopus	19
РИНЦ	19
OpenAlex	21