Activation of Bis(phenoxyimino)zirconium Polymerization Catalysts with Methylaluminoxane and AlMe3/[CPh3]+[B(C6F5)4]- Full article
| Journal |
Organometallics
ISSN: 0276-7333 , E-ISSN: 1520-6041 |
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| Output data | Year: 2007, Volume: 26, Number: 19, Pages: 4810-4815 Pages count : 6 DOI: 10.1021/om7004113 | ||||
| Tags | Catalyst activity; Nuclear magnetic resonance spectroscopy; Polymerization; Zirconium compounds | ||||
| Authors |
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| Affiliations |
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Funding (2)
| 1 | Russian Foundation for Basic Research | 06-03-32700 |
| 2 | Royal Society | 2004/R1-FSU |
Abstract:
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.
Cite:
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 ANCAN OpenAlex
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 ANCAN OpenAlex
Dates:
| Submitted: | Apr 27, 2007 |
| Published online: | Aug 8, 2007 |
| Published print: | Sep 1, 2007 |
Identifiers:
| Web of science: | WOS:000249242100019 |
| Scopus: | 2-s2.0-34748829738 |
| Elibrary: | 13559333 |
| Chemical Abstracts: | 2007:865432 |
| Chemical Abstracts (print): | 147:427724 |
| OpenAlex: | W1986164918 |