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Article: Neutron and X-ray diffraction and spectroscopic investigations of intramolecular [C-H⋯F-C] contacts in post-metallocene polyolefin catalysts: Modeling weak attractive polymer-ligand interactions

TitleNeutron and X-ray diffraction and spectroscopic investigations of intramolecular [C-H⋯F-C] contacts in post-metallocene polyolefin catalysts: Modeling weak attractive polymer-ligand interactions
Authors
KeywordsFluorinated ligands
Hydrogen bonds
Neutron diffraction
Noncovalent interactions
Post-metallocenes
Issue Date2006
PublisherWiley - V C H Verlag GmbH & Co KGaA. The Journal's web site is located at http://www.wiley-vch.de/home/chemistry
Citation
Chemistry - A European Journal, 2006, v. 12 n. 9, p. 2607-2619 How to Cite?
AbstractA family of Group 4 post-metallocene catalysts, supported by fluorine-functionalized tridentate ligands with the fluorine substituent in the locality of the metal center, is described. For the first time, the contentious C-H⋯F-C interaction has been characterized by a neutron diffraction study, which has allowed the position of the hydrogen atoms to be accurately determined. The nature of the weak intramolecular C-H⋯F-C contacts in these complexes in solution and the solid state was probed by using multinuclear NMR spectroscopy in tandem with neutron and X-ray crystallography. Evidence is presented to demonstrate that the spectroscopic C-H⋯F-C coupling occurs "through-space" rather than "through-bond" or by M⋯F coordination. The titanium catalysts exhibit excellent activities and high co-monomer incorporation in olefin polymerization. The observed intramolecular C-H⋯F-C interactions are important with regards to potential applications in polyolefin catalysis because they substantiate the proposed ortho-F⋯H(β) ligand-(polymer chain) contacts derived from DFT calculations for the remarkable fluorinated phenoxyimine Group 4 catalysts. Compared with agostic and co-catalyst⋯metal contacts, weak attractive noncovalent interactions between a polymer chain and a judiciously designed "active" ligand is a new concept in polyolefin catalysis. © 2006 Wiley-VCH Verlag GmbH & Co. KGaA.
Persistent Identifierhttp://hdl.handle.net/10722/69284
ISSN
2015 Impact Factor: 5.771
2015 SCImago Journal Rankings: 2.323
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorChan, MCWen_HK
dc.contributor.authorKui, SCFen_HK
dc.contributor.authorCole, JMen_HK
dc.contributor.authorMcIntyre, GJen_HK
dc.contributor.authorMatsui, Sen_HK
dc.contributor.authorZhu, Nen_HK
dc.contributor.authorTam, KHen_HK
dc.date.accessioned2010-09-06T06:12:15Z-
dc.date.available2010-09-06T06:12:15Z-
dc.date.issued2006en_HK
dc.identifier.citationChemistry - A European Journal, 2006, v. 12 n. 9, p. 2607-2619en_HK
dc.identifier.issn0947-6539en_HK
dc.identifier.urihttp://hdl.handle.net/10722/69284-
dc.description.abstractA family of Group 4 post-metallocene catalysts, supported by fluorine-functionalized tridentate ligands with the fluorine substituent in the locality of the metal center, is described. For the first time, the contentious C-H⋯F-C interaction has been characterized by a neutron diffraction study, which has allowed the position of the hydrogen atoms to be accurately determined. The nature of the weak intramolecular C-H⋯F-C contacts in these complexes in solution and the solid state was probed by using multinuclear NMR spectroscopy in tandem with neutron and X-ray crystallography. Evidence is presented to demonstrate that the spectroscopic C-H⋯F-C coupling occurs "through-space" rather than "through-bond" or by M⋯F coordination. The titanium catalysts exhibit excellent activities and high co-monomer incorporation in olefin polymerization. The observed intramolecular C-H⋯F-C interactions are important with regards to potential applications in polyolefin catalysis because they substantiate the proposed ortho-F⋯H(β) ligand-(polymer chain) contacts derived from DFT calculations for the remarkable fluorinated phenoxyimine Group 4 catalysts. Compared with agostic and co-catalyst⋯metal contacts, weak attractive noncovalent interactions between a polymer chain and a judiciously designed "active" ligand is a new concept in polyolefin catalysis. © 2006 Wiley-VCH Verlag GmbH & Co. KGaA.en_HK
dc.languageengen_HK
dc.publisherWiley - V C H Verlag GmbH & Co KGaA. The Journal's web site is located at http://www.wiley-vch.de/home/chemistryen_HK
dc.relation.ispartofChemistry - A European Journalen_HK
dc.subjectFluorinated ligandsen_HK
dc.subjectHydrogen bondsen_HK
dc.subjectNeutron diffractionen_HK
dc.subjectNoncovalent interactionsen_HK
dc.subjectPost-metallocenesen_HK
dc.titleNeutron and X-ray diffraction and spectroscopic investigations of intramolecular [C-H⋯F-C] contacts in post-metallocene polyolefin catalysts: Modeling weak attractive polymer-ligand interactionsen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0947-6539&volume=12&issue=9&spage=2607&epage=2619&date=2006&atitle=Neutron+and+X-ray+diffraction+and+spectroscopic+investigations+of+intramolecular+[C-H⋯F-C]+contacts+in+post-metallocene+polyolefin+catalysts:+modeling+weak+attractive+polymer-ligand+interactionsen_HK
dc.identifier.emailKui, SCF: stevenku@hku.hken_HK
dc.identifier.emailZhu, N: nzhu@hkucc.hku.hken_HK
dc.identifier.authorityKui, SCF=rp00715en_HK
dc.identifier.authorityZhu, N=rp00845en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1002/chem.200501054en_HK
dc.identifier.pmid16363010-
dc.identifier.scopuseid_2-s2.0-33644911451en_HK
dc.identifier.hkuros126543en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-33644911451&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume12en_HK
dc.identifier.issue9en_HK
dc.identifier.spage2607en_HK
dc.identifier.epage2619en_HK
dc.identifier.isiWOS:000236257800023-
dc.publisher.placeGermanyen_HK
dc.identifier.scopusauthoridChan, MCW=7402598116en_HK
dc.identifier.scopusauthoridKui, SCF=6506763660en_HK
dc.identifier.scopusauthoridCole, JM=7403376199en_HK
dc.identifier.scopusauthoridMcIntyre, GJ=7102465973en_HK
dc.identifier.scopusauthoridMatsui, S=7401853971en_HK
dc.identifier.scopusauthoridZhu, N=7201449530en_HK
dc.identifier.scopusauthoridTam, KH=7201692833en_HK

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