F-19 chemical shifts, coupling constants and conformational preferences in monosubstituted perfluoroparacyclophanes

dc.creatorGhiviriga, I
dc.creatorZhang, LH
dc.creatorMartinez, H
dc.creatorContreras, RH
dc.creatorTormena, CF
dc.creatorNodin, L
dc.creatorDolbier, WR
dc.date2011
dc.dateMAR
dc.date2014-07-30T17:34:20Z
dc.date2015-11-26T17:28:52Z
dc.date2014-07-30T17:34:20Z
dc.date2015-11-26T17:28:52Z
dc.date.accessioned2018-03-29T00:15:56Z
dc.date.available2018-03-29T00:15:56Z
dc.identifierMagnetic Resonance In Chemistry. Wiley-blackwell, v. 49, n. 3, n. 93, n. 105, 2011.
dc.identifier0749-1581
dc.identifierWOS:000287890600001
dc.identifier10.1002/mrc.2713
dc.identifierhttp://www.repositorio.unicamp.br/jspui/handle/REPOSIP/66629
dc.identifierhttp://repositorio.unicamp.br/jspui/handle/REPOSIP/66629
dc.identifier.urihttp://repositorioslatinoamericanos.uchile.cl/handle/2250/1285153
dc.descriptionFundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
dc.descriptionIn the process of studying the chemistry of perfluoro[2.2]paracyclophanes (PFPCs), a novel class of compounds, it became necessary to identify some disubstituted products. To achieve this goal, we characterize in this work some monosubstituted PFPCs, identifying their F-19-F-19 coupling patterns, and establishing a methodology for the assignment of their F-19 chemical shifts. The pattern of coupling constants indicates a skewed geometry in which the upper deck moves towards or away from the substituent, depending on the substituent electron-donor character and size. Quantum chemical calculations, performed at the HF/6-311 + G(d,p)//B3LYP/EPR-III level of theory, confirmed the conformations inferred from coupling constants and reproduced well the values of the couplings. Transmission mechanisms for the FC term of four- and five-bond F-19-F-19 couplings are discussed in detail. Understanding the conformational preferences of PFPCs and how they are reflected by the coupling constants facilitates the assignment of F-19 chemical shifts in monosubstituted PFPCs and the identification of the disubstituted products. Copyright (C) 2011 John Wiley & Sons, Ltd.
dc.description49
dc.description3
dc.description93
dc.description105
dc.descriptionCONICET [5119/05]
dc.descriptionUBACYT [X-047]
dc.descriptionFundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
dc.descriptionFundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
dc.descriptionCONICET [5119/05]
dc.descriptionUBACYT [X-047]
dc.descriptionFAPESP [06/03980-2, 08/06282-0]
dc.languageen
dc.publisherWiley-blackwell
dc.publisherMalden
dc.publisherEUA
dc.relationMagnetic Resonance In Chemistry
dc.relationMagn. Reson. Chem.
dc.rightsfechado
dc.rightshttp://olabout.wiley.com/WileyCDA/Section/id-406071.html
dc.sourceWeb of Science
dc.subjectNMR
dc.subjectF-19-F-19 couplings
dc.subjectF-19 chemical shifts
dc.subjectperfluoro[2.2]paracyclophane
dc.subjectparacyclophane
dc.subjectconformation
dc.subjectFCCP-CMO
dc.subjectFermi hole
dc.subjectthrough-space
dc.subjectPolarization Propagator Analysis
dc.subjectThrough-space Transmission
dc.subjectNonbonded Interactions
dc.subjectMolecular-orbitals
dc.subjectAngular-dependence
dc.subjectScalar Couplings
dc.subjectLone Pairs
dc.subjectSpin
dc.subjectMechanisms
dc.subjectBond
dc.titleF-19 chemical shifts, coupling constants and conformational preferences in monosubstituted perfluoroparacyclophanes
dc.typeArtículos de revistas


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