Structure-catalytic activity relationship in bridging silacycloalkyl ring conformations of constrained geometry titanium complexes
DC Field | Value | Language |
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dc.contributor.author | Kang, Eugene | - |
dc.contributor.author | Kim, Sung-Kwan | - |
dc.contributor.author | Kim, Tae-Jin | - |
dc.contributor.author | Chung, Jae-Ho | - |
dc.contributor.author | Hahn, Jong Sok | - |
dc.contributor.author | Ko, Jaejung | - |
dc.contributor.author | Ok, Myung-Ahn | - |
dc.contributor.author | Cheong, Minserk | - |
dc.contributor.author | Kang, Sang Ook | - |
dc.date.accessioned | 2022-01-08T10:41:32Z | - |
dc.date.available | 2022-01-08T10:41:32Z | - |
dc.date.created | 2021-08-30 | - |
dc.date.issued | 2008-05 | - |
dc.identifier.issn | 1434-1948 | - |
dc.identifier.uri | https://scholar.korea.ac.kr/handle/2021.sw.korea/134874 | - |
dc.description.abstract | A series of cyclic silylene-bridged (amidocyclopentadienyl)-dichlorotitanium(IV) complexes [TiCl2{eta(5)-1-(CySitBuN-kappa N)-2,3,4,5-R-4-C-5}] was prepared, where CySi = silacyclobutyl (a), silacyclopentenyl (b), silacyclopentyl (c), and silacyclohexyl (d); R = H (4), Me (5). The starting silane, dichloro-silacycloalkane CySiCl2 (1), was treated with NaCp (LiCp*), followed by LiNHtBu to yield the cyclic silylene-bridged ligands (R4C5)CySi(NHtBu) [R = H (2); Me (3)]. Subsequent deprotonation with n-butyllithium, followed by transmetalation with TiCl4 yielded the desired constrained geometry complexes (CGCs) (CpCySiNtBu)TiCl2 (4) and (Cp*CySiNtBu)TiCl2 (5). The structures of the resulting cyclopentadienyl- (4b and 4c) and tetramethylcyclopentadienyl(silacycloalkyl)amidotitanium(IV) dichloride (5a, 5c, and 5d) species were studied by using X-ray crystallography to obtain geometrical information on cyclic silylene-modified CGCs. The ethylene polymerization by the cyclic silylene-bridged CGCs 4 and 5 was examined to verify the structure-catalytic activity relationship derived from variation of the size of a cyclic silylene ring. Indeed, the size of the cyclic silylene ring at the 1,1'-position of 4 and 5 affected the catalytic activities through the ethylene polymerization. Systematic increase in the catalytic activities was observed as the cyclic silylene-bridging unit was expanded from a four- to six-membered ring. In the present study, we found that CGCs of Ti-IV with a six-membered silylene-bridged ligand (5d) produced active catalytic species for the formation of polyethylene with M-W = 42.7 X 10(-4) g mol(-1) and M-W/M-n = 2.1 with excellent catalytic activities (20.9 kgpolymer per mmol of Ti). When titanium(IV) dimethyl complex (6d) was applied in continuous polymerization process, impressive high catalytic activity on copolymerization with 1-octene was observed. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim., Germany, 2008). | - |
dc.language | English | - |
dc.language.iso | en | - |
dc.publisher | WILEY-V C H VERLAG GMBH | - |
dc.subject | GROUP-4 METAL-COMPLEXES | - |
dc.subject | HALF-SANDWICH COMPLEXES | - |
dc.subject | ANSA-METALLOCENE COMPLEXES | - |
dc.subject | FOCK-SLATER CALCULATIONS | - |
dc.subject | OLEFIN POLYMERIZATION | - |
dc.subject | CYCLOPENTADIENYL LIGANDS | - |
dc.subject | SINGLE-SITE | - |
dc.subject | ZIRCONIUM COMPLEXES | - |
dc.subject | BINUCLEAR CATALYSTS | - |
dc.subject | INDENYL COMPLEXES | - |
dc.title | Structure-catalytic activity relationship in bridging silacycloalkyl ring conformations of constrained geometry titanium complexes | - |
dc.type | Article | - |
dc.contributor.affiliatedAuthor | Kang, Sang Ook | - |
dc.identifier.doi | 10.1002/ejic.200701312 | - |
dc.identifier.scopusid | 2-s2.0-53249111650 | - |
dc.identifier.wosid | 000255854400013 | - |
dc.identifier.bibliographicCitation | EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, no.13, pp.2214 - 2224 | - |
dc.relation.isPartOf | EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | - |
dc.citation.title | EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | - |
dc.citation.number | 13 | - |
dc.citation.startPage | 2214 | - |
dc.citation.endPage | 2224 | - |
dc.type.rims | ART | - |
dc.type.docType | Review | - |
dc.description.journalClass | 1 | - |
dc.description.journalRegisteredClass | scie | - |
dc.description.journalRegisteredClass | scopus | - |
dc.relation.journalResearchArea | Chemistry | - |
dc.relation.journalWebOfScienceCategory | Chemistry, Inorganic & Nuclear | - |
dc.subject.keywordPlus | GROUP-4 METAL-COMPLEXES | - |
dc.subject.keywordPlus | HALF-SANDWICH COMPLEXES | - |
dc.subject.keywordPlus | ANSA-METALLOCENE COMPLEXES | - |
dc.subject.keywordPlus | FOCK-SLATER CALCULATIONS | - |
dc.subject.keywordPlus | OLEFIN POLYMERIZATION | - |
dc.subject.keywordPlus | CYCLOPENTADIENYL LIGANDS | - |
dc.subject.keywordPlus | SINGLE-SITE | - |
dc.subject.keywordPlus | ZIRCONIUM COMPLEXES | - |
dc.subject.keywordPlus | BINUCLEAR CATALYSTS | - |
dc.subject.keywordPlus | INDENYL COMPLEXES | - |
dc.subject.keywordAuthor | Si ligands | - |
dc.subject.keywordAuthor | cyclopentadienyl ligands | - |
dc.subject.keywordAuthor | titanium | - |
dc.subject.keywordAuthor | isomers | - |
dc.subject.keywordAuthor | structure-activity relationships | - |
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