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dc.contributor.authorNazarski, Ryszard B.
dc.contributor.authorMakulski, Włodzimierz
dc.identifier.citationR. B. Nazarski, W. Makulski, 1JCH couplings in Group14/IVA tetramethyls from the gas-phase NMR and DFT structural study: a search for the best computational protocol in Physical Chemistry Chemical Physics;2014, DOI: 10.1039/C4CP01596Gpl_PL
dc.identifier.otherDOI: 10.1039/C4CP01596G
dc.identifier.otherESSN: 1463-9084
dc.descriptionAccepted Manuscriptpl_PL
dc.description.abstractFour tetramethyl compounds EMe4 (E = C, Si, Ge, and Pb) were studied by high-resolution NMR spectroscopy in gaseous and liquid states at 300 K. Extrapolation of experimental vapor-phase C-H J-couplings to a zero-pressure limit permitted determining the 1J0,CHs in methyl groups of their nearly isolated molecules. Theoretical predictions of the latter NMR parameters were also performed in a locally dense basis sets/pseudopotential (Sn, Pb) approach, by applying a few DFT methods pre-selected in calculations of other gas-phase molecular properties of all these species and SnMe4 (bond lengths, C-H stretching IR vibrations). A very good agreement theory vs. experiment was achieved with some computational protocols for the all five systems. The trends observed in their geometry and associated coupling constants (1JCHs, 2JHHs) are discussed and rationalized in terms of the substituent-induced rehybridization of the methyl group (treated as a ligand) carbon, by using Bent’s rule and newly proposed, theoretically derived values of the Mulliken electronegativity (χ) of related atoms and groups. All these χ data for the Group-14/IVA entities were under a lot of controversy for a very long time. As a result, the recommended χ values are semi-experimentally confirmed for the first time and only a small correction is suggested for χ(Ge) and χ(GeMe3).pl_PL
dc.description.sponsorshipPublikacja w ramach programu Royal Society of Chemistry "Gold for Gold" 2014 finansowanego przez Uniwersytet Łódzkipl_PL
dc.publisherThe Royal Society of Chemistrypl_PL
dc.relation.ispartofseriesPhysical Chemistry Chemical Physics;2014
dc.rightsUznanie autorstwa-Użycie niekomercyjne 3.0 Polska*
dc.subjecttetramethyl compoundspl_PL
dc.subjectcarbon familypl_PL
dc.subjecttin and lead organoderivativespl_PL
dc.subjectgas-phase NMR spectrapl_PL
dc.subjectmolecular propertiespl_PL
dc.subjectcarbon-proton coupling constantspl_PL
dc.subjectlocal dense basis setspl_PL
dc.subjectBent’s rulepl_PL
dc.subjectMulliken electronegativitypl_PL
dc.subjecttetrahedral distortionpl_PL
dc.title1JCH couplings in Group14/IVA tetramethyls from the gas-phase NMR and DFT structural study: a search for the best computational protocolpl_PL
dc.contributor.authorAffiliationRyszard B. Nazarski - University of Łódź, Faculty of Chemistry, Laboratory of Molecular Spectroscopypl_PL
dc.contributor.authorAffiliationWłodzimierz Makulski - University of Warsaw, Faculty of Chemistry, Laboratory of NMR Spectroscopypl_PL

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Uznanie autorstwa-Użycie niekomercyjne 3.0 Polska
Except where otherwise noted, this item's license is described as Uznanie autorstwa-Użycie niekomercyjne 3.0 Polska