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Article: Synthesis, structures, and olefin polymerization characteristics of group 4 catalysts [Zr{(OAr)2py}Cl2(D)] (D = O-donors, Cl[HPR 3]) supported by tridentate pyridine-2,6-bis(aryloxide) ligands

TitleSynthesis, structures, and olefin polymerization characteristics of group 4 catalysts [Zr{(OAr)2py}Cl2(D)] (D = O-donors, Cl[HPR 3]) supported by tridentate pyridine-2,6-bis(aryloxide) ligands
Authors
Issue Date2006
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/organometallics
Citation
Organometallics, 2006, v. 25 n. 3, p. 785-792 How to Cite?
AbstractThe Zr(IV) complexes [Zr(L1)X2(D)] [H 2L1 = 2,6-di(3-tert-butyl-5-methylphen-2-ol)pyridine; X = Cl, D = thf (1), OEt2 (2), acetophenone (3), benzophenone (4), 2-acetonaphthone (5), Cl[fHPR3] {R = Me (6), Et (7); R3 = Me2Ph (8)}; X = CH2Ph (9)] have been synthesized, and the crystal structures of 3, 4, and 7 have been determined. These catalysts, assisted by the robustness and chelating strength of the pyridine-bis(phenolate) moiety, exhibit excellent activities for ethylene polymerization in conjunction with MAO. Studies to assess the impact of the donor group during the catalytic process suggest that the same active species is generated by 1-8/MAO and the donor group does not play an active role. Even higher activities are observed for the 1/iBu3Al/Ph3CB(C6F5) 4 system in ethylene polymerization and propylene copolymerization reactions (36 590 and 15 700 g of polymer (mmol of catalyst)-1 h -1, respectively), with the latter displaying good C3 incorporation (25.4 mol % C3). Insight into the catalytic behavior of the 1/MAO system has been derived from GPC and NMR characterization of the polymers prepared under different reaction conditions. 1H and 13C NMR end-group analyses reveal resonances for saturated methyl chain-end groups only and undetectable or negligible levels of unsaturated vinyl chain ends. This indicates that for the polymerization chain-transfer mechanism, the conventional β-H transfer reactions to the metal/monomer are insignificant and the unusual chain transfer to Al pathway is vastly dominant. © 2006 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/168005
ISSN
2015 Impact Factor: 4.186
2015 SCImago Journal Rankings: 2.043
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorChan, MCWen_HK
dc.contributor.authorTam, KHen_HK
dc.contributor.authorZhu, Nen_HK
dc.contributor.authorChiu, Pen_HK
dc.contributor.authorMatsui, Sen_HK
dc.date.accessioned2012-10-08T03:14:01Z-
dc.date.available2012-10-08T03:14:01Z-
dc.date.issued2006en_HK
dc.identifier.citationOrganometallics, 2006, v. 25 n. 3, p. 785-792en_HK
dc.identifier.issn0276-7333en_HK
dc.identifier.urihttp://hdl.handle.net/10722/168005-
dc.description.abstractThe Zr(IV) complexes [Zr(L1)X2(D)] [H 2L1 = 2,6-di(3-tert-butyl-5-methylphen-2-ol)pyridine; X = Cl, D = thf (1), OEt2 (2), acetophenone (3), benzophenone (4), 2-acetonaphthone (5), Cl[fHPR3] {R = Me (6), Et (7); R3 = Me2Ph (8)}; X = CH2Ph (9)] have been synthesized, and the crystal structures of 3, 4, and 7 have been determined. These catalysts, assisted by the robustness and chelating strength of the pyridine-bis(phenolate) moiety, exhibit excellent activities for ethylene polymerization in conjunction with MAO. Studies to assess the impact of the donor group during the catalytic process suggest that the same active species is generated by 1-8/MAO and the donor group does not play an active role. Even higher activities are observed for the 1/iBu3Al/Ph3CB(C6F5) 4 system in ethylene polymerization and propylene copolymerization reactions (36 590 and 15 700 g of polymer (mmol of catalyst)-1 h -1, respectively), with the latter displaying good C3 incorporation (25.4 mol % C3). Insight into the catalytic behavior of the 1/MAO system has been derived from GPC and NMR characterization of the polymers prepared under different reaction conditions. 1H and 13C NMR end-group analyses reveal resonances for saturated methyl chain-end groups only and undetectable or negligible levels of unsaturated vinyl chain ends. This indicates that for the polymerization chain-transfer mechanism, the conventional β-H transfer reactions to the metal/monomer are insignificant and the unusual chain transfer to Al pathway is vastly dominant. © 2006 American Chemical Society.en_HK
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/organometallicsen_HK
dc.relation.ispartofOrganometallicsen_HK
dc.titleSynthesis, structures, and olefin polymerization characteristics of group 4 catalysts [Zr{(OAr)2py}Cl2(D)] (D = O-donors, Cl[HPR 3]) supported by tridentate pyridine-2,6-bis(aryloxide) ligandsen_HK
dc.typeArticleen_HK
dc.identifier.emailZhu, N: nzhu@hkucc.hku.hken_HK
dc.identifier.emailChiu, P: pchiu@hku.hken_HK
dc.identifier.authorityZhu, N=rp00845en_HK
dc.identifier.authorityChiu, P=rp00680en_HK
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/om050864zen_HK
dc.identifier.scopuseid_2-s2.0-33644506431en_HK
dc.identifier.hkuros130376-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-33644506431&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume25en_HK
dc.identifier.issue3en_HK
dc.identifier.spage785en_HK
dc.identifier.epage792en_HK
dc.identifier.isiWOS:000234906900029-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridChan, MCW=7402598116en_HK
dc.identifier.scopusauthoridTam, KH=7201692833en_HK
dc.identifier.scopusauthoridZhu, N=7201449530en_HK
dc.identifier.scopusauthoridChiu, P=11140148700en_HK
dc.identifier.scopusauthoridMatsui, S=7401853971en_HK

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