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Article: Scalar Coupling Across [C-H⋯F-C] Interactions in (σ-Aryl)-Chelating Post-Metallocenes

TitleScalar Coupling Across [C-H⋯F-C] Interactions in (σ-Aryl)-Chelating Post-Metallocenes
Authors
Keywordsfluorinated ligands
hydrogen bonds
neighboring-group effects
noncovalent interactions
post-metallocenes
Issue Date2012
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, 2012, v. 18 n. 2, p. 565-573 How to Cite?
AbstractThe nature and importance of C-H⋯F-C interactions is a topical yet controversial issue, and the development of spectroscopic methods to probe such contacts is therefore warranted. A series of Group 4 bis(benzyl) complexes supported by (σ-aryl)-2-phenolate-6-pyridyl [O,C,N-R 1] ligands bearing a fluorinated R 1 group (CF 3 or F) in the vicinity of the metal has been prepared. The X-ray crystal structure of the CF 3-substituted Hf derivative features intramolecular C-H⋯F-C and Hf⋯F-C contacts. All complexes have been characterized by multinuclear NMR spectroscopy. The 1H and 13C NMR spectra of [M(O,C,N-CF 3)(CH 2Ph) 2] derivatives display coupling (assigned to 1hJ HF and 2hJ CF for Ti; 3J HF and 2J CF (through M⋯F) for Hf and Zr) between the benzyl CH 2 and CF 3 moieties. [ 1H, 19F]-HMBC NMR experiments have been performed for the M-[O,C,N-R 1] complexes and their [O,N,C] counterparts, revealing significant scalar coupling across the C-H⋯F-C interactions for Ti-[O,C,N] and [O,N,C] species. Genuinely attractive! The titled complexes have been characterized by multinuclear NMR (including [ 1H, 19F]-HMBC) experiments, which for the first time confirm that the observed 1H- 19F coupling occurs with chemical connectivity across C-H⋯F-C interactions for Ti complexes (see scheme); differences in coupling patterns for Zr and Hf congeners are also rationalized. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Persistent Identifierhttp://hdl.handle.net/10722/157667
ISSN
2015 Impact Factor: 5.771
2015 SCImago Journal Rankings: 2.323
ISI Accession Number ID
Funding AgencyGrant Number
Research Grants Council of the Hong Kong SAR, ChinaCityU 100406
Funding Information:

The work described in this paper was wholly supported by the Research Grants Council of the Hong Kong SAR, China (CityU 100406).

References

 

DC FieldValueLanguage
dc.contributor.authorSo, LCen_HK
dc.contributor.authorLiu, CCen_HK
dc.contributor.authorChan, MCWen_HK
dc.contributor.authorLo, JCYen_HK
dc.contributor.authorSze, KHen_HK
dc.contributor.authorZhu, Nen_HK
dc.date.accessioned2012-08-08T08:52:05Z-
dc.date.available2012-08-08T08:52:05Z-
dc.date.issued2012en_HK
dc.identifier.citationChemistry - A European Journal, 2012, v. 18 n. 2, p. 565-573en_HK
dc.identifier.issn0947-6539en_HK
dc.identifier.urihttp://hdl.handle.net/10722/157667-
dc.description.abstractThe nature and importance of C-H⋯F-C interactions is a topical yet controversial issue, and the development of spectroscopic methods to probe such contacts is therefore warranted. A series of Group 4 bis(benzyl) complexes supported by (σ-aryl)-2-phenolate-6-pyridyl [O,C,N-R 1] ligands bearing a fluorinated R 1 group (CF 3 or F) in the vicinity of the metal has been prepared. The X-ray crystal structure of the CF 3-substituted Hf derivative features intramolecular C-H⋯F-C and Hf⋯F-C contacts. All complexes have been characterized by multinuclear NMR spectroscopy. The 1H and 13C NMR spectra of [M(O,C,N-CF 3)(CH 2Ph) 2] derivatives display coupling (assigned to 1hJ HF and 2hJ CF for Ti; 3J HF and 2J CF (through M⋯F) for Hf and Zr) between the benzyl CH 2 and CF 3 moieties. [ 1H, 19F]-HMBC NMR experiments have been performed for the M-[O,C,N-R 1] complexes and their [O,N,C] counterparts, revealing significant scalar coupling across the C-H⋯F-C interactions for Ti-[O,C,N] and [O,N,C] species. Genuinely attractive! The titled complexes have been characterized by multinuclear NMR (including [ 1H, 19F]-HMBC) experiments, which for the first time confirm that the observed 1H- 19F coupling occurs with chemical connectivity across C-H⋯F-C interactions for Ti complexes (see scheme); differences in coupling patterns for Zr and Hf congeners are also rationalized. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.en_HK
dc.languageengen_US
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.subjectneighboring-group effectsen_HK
dc.subjectnoncovalent interactionsen_HK
dc.subjectpost-metallocenesen_HK
dc.subject.meshCarbon - Chemistryen_US
dc.subject.meshChelating Agents - Chemistryen_US
dc.subject.meshCrystallography, X-Rayen_US
dc.subject.meshFluorine - Chemistryen_US
dc.subject.meshHydrogen Bondingen_US
dc.subject.meshLigandsen_US
dc.subject.meshModels, Molecularen_US
dc.subject.meshOrganometallic Compounds - Chemistryen_US
dc.titleScalar Coupling Across [C-H⋯F-C] Interactions in (σ-Aryl)-Chelating Post-Metallocenesen_HK
dc.typeArticleen_HK
dc.identifier.emailSze, KH: khsze@hku.hken_HK
dc.identifier.emailZhu, N: nzhu@hkucc.hku.hken_HK
dc.identifier.authoritySze, KH=rp00785en_HK
dc.identifier.authorityZhu, N=rp00845en_HK
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1002/chem.201102439en_HK
dc.identifier.pmid22161818-
dc.identifier.scopuseid_2-s2.0-84855328194en_HK
dc.identifier.hkuros211862-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-84855328194&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume18en_HK
dc.identifier.issue2en_HK
dc.identifier.spage565en_HK
dc.identifier.epage573en_HK
dc.identifier.isiWOS:000298731200023-
dc.publisher.placeGermanyen_HK
dc.identifier.scopusauthoridSo, LC=54882038600en_HK
dc.identifier.scopusauthoridLiu, CC=54882127900en_HK
dc.identifier.scopusauthoridChan, MCW=29067669100en_HK
dc.identifier.scopusauthoridLo, JCY=36742777100en_HK
dc.identifier.scopusauthoridSze, KH=7006735061en_HK
dc.identifier.scopusauthoridZhu, N=7201449530en_HK

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