Matches in SemOpenAlex for { <https://semopenalex.org/work/W2023648202> ?p ?o ?g. }
Showing items 1 to 86 of
86
with 100 items per page.
- W2023648202 endingPage "1153" @default.
- W2023648202 startingPage "1144" @default.
- W2023648202 abstract "Nonempirical SCF-MO computations have been performed on CH 2 O, CH 2 S, and their protonated derivatives [Formula: see text] and [Formula: see text]. The methylene group of CH 2 O is strongly positive and that of CH 2 S is slightly negative, because oxygen in CH 2 O behaves towards carbon as a π-donor and σ-acceptor, but sulfur in CH 2 S behaves as both a π- and σ-donor. The total π-overlap in CH 2 O is greater than that in CH 2 S.The stable conformations of [Formula: see text] and [Formula: see text] correspond in each case to a structure in which all atoms lie in the same plane. In this conformation, both the C—O and C—S bond lengths are substantially shorter than those of methanol and methanethiol, indicative of conjugative interaction between the cationic center and the adjacent heteroatom. From the results of a Mulliken-type population analysis it is found that, relative to hydrogen, OH and SH behave towards an adjacent [Formula: see text] group as electron-withdrawing and electron-releasing ligands, respectively. When [Formula: see text] is considered to form from [Formula: see text] and OH fragments, π-donation from O to C amounts to 0.38 electron, but σ-donation in the opposite direction amounts to 0.35 electron; the π-overlap population is 0.1496. A similar analysis of [Formula: see text] reveals π- and σ-donation from S to C of 0.53 and 0.15 electron, respectively, and a π-overlap population of 0.1734, so that sulfurformsastronger π-bondtotheadjacentcationiccenter.Geometrical isomerization of [Formula: see text] proceeds by linear inversion at oxygen, with a barrier of 13.98 kcal/mol; but that of [Formula: see text] proceeds by rotation about the C—S bond, with a barrier of 36.47 kcal/mol. This latter value is substantially higher than that (23 kcal/mol ) computed for [Formula: see text] with a rigid rotor model, and reflects the greater strength of the π-bond between sulfur and the adjacent cationic center." @default.
- W2023648202 created "2016-06-24" @default.
- W2023648202 creator A5036170744 @default.
- W2023648202 creator A5062087824 @default.
- W2023648202 creator A5072645125 @default.
- W2023648202 creator A5074423254 @default.
- W2023648202 date "1975-04-15" @default.
- W2023648202 modified "2023-10-18" @default.
- W2023648202 title "On the π-Donating Abilities of Sulfur and Oxygen. A Comparative Quantum Chemical Investigation of the Static and Dynamic Properties and Gas Phase Acidities of and" @default.
- W2023648202 cites W608850903 @default.
- W2023648202 doi "https://doi.org/10.1139/v75-159" @default.
- W2023648202 hasPublicationYear "1975" @default.
- W2023648202 type Work @default.
- W2023648202 sameAs 2023648202 @default.
- W2023648202 citedByCount "48" @default.
- W2023648202 countsByYear W20236482022019 @default.
- W2023648202 countsByYear W20236482022022 @default.
- W2023648202 crossrefType "journal-article" @default.
- W2023648202 hasAuthorship W2023648202A5036170744 @default.
- W2023648202 hasAuthorship W2023648202A5062087824 @default.
- W2023648202 hasAuthorship W2023648202A5072645125 @default.
- W2023648202 hasAuthorship W2023648202A5074423254 @default.
- W2023648202 hasBestOaLocation W20236482021 @default.
- W2023648202 hasConcept C121332964 @default.
- W2023648202 hasConcept C144024400 @default.
- W2023648202 hasConcept C145148216 @default.
- W2023648202 hasConcept C147120987 @default.
- W2023648202 hasConcept C147597530 @default.
- W2023648202 hasConcept C149923435 @default.
- W2023648202 hasConcept C152365726 @default.
- W2023648202 hasConcept C155647269 @default.
- W2023648202 hasConcept C178790620 @default.
- W2023648202 hasConcept C185592680 @default.
- W2023648202 hasConcept C196609583 @default.
- W2023648202 hasConcept C20950531 @default.
- W2023648202 hasConcept C2777454769 @default.
- W2023648202 hasConcept C2780378348 @default.
- W2023648202 hasConcept C2900893 @default.
- W2023648202 hasConcept C2908647359 @default.
- W2023648202 hasConcept C30095370 @default.
- W2023648202 hasConcept C62520636 @default.
- W2023648202 hasConcept C71240020 @default.
- W2023648202 hasConcept C7214806 @default.
- W2023648202 hasConcept C8010536 @default.
- W2023648202 hasConceptScore W2023648202C121332964 @default.
- W2023648202 hasConceptScore W2023648202C144024400 @default.
- W2023648202 hasConceptScore W2023648202C145148216 @default.
- W2023648202 hasConceptScore W2023648202C147120987 @default.
- W2023648202 hasConceptScore W2023648202C147597530 @default.
- W2023648202 hasConceptScore W2023648202C149923435 @default.
- W2023648202 hasConceptScore W2023648202C152365726 @default.
- W2023648202 hasConceptScore W2023648202C155647269 @default.
- W2023648202 hasConceptScore W2023648202C178790620 @default.
- W2023648202 hasConceptScore W2023648202C185592680 @default.
- W2023648202 hasConceptScore W2023648202C196609583 @default.
- W2023648202 hasConceptScore W2023648202C20950531 @default.
- W2023648202 hasConceptScore W2023648202C2777454769 @default.
- W2023648202 hasConceptScore W2023648202C2780378348 @default.
- W2023648202 hasConceptScore W2023648202C2900893 @default.
- W2023648202 hasConceptScore W2023648202C2908647359 @default.
- W2023648202 hasConceptScore W2023648202C30095370 @default.
- W2023648202 hasConceptScore W2023648202C62520636 @default.
- W2023648202 hasConceptScore W2023648202C71240020 @default.
- W2023648202 hasConceptScore W2023648202C7214806 @default.
- W2023648202 hasConceptScore W2023648202C8010536 @default.
- W2023648202 hasIssue "8" @default.
- W2023648202 hasLocation W20236482021 @default.
- W2023648202 hasOpenAccess W2023648202 @default.
- W2023648202 hasPrimaryLocation W20236482021 @default.
- W2023648202 hasRelatedWork W2014602804 @default.
- W2023648202 hasRelatedWork W2023648202 @default.
- W2023648202 hasRelatedWork W2026346666 @default.
- W2023648202 hasRelatedWork W2033589463 @default.
- W2023648202 hasRelatedWork W2157006537 @default.
- W2023648202 hasRelatedWork W2398000188 @default.
- W2023648202 hasRelatedWork W2626897852 @default.
- W2023648202 hasRelatedWork W2953264190 @default.
- W2023648202 hasRelatedWork W2973125323 @default.
- W2023648202 hasRelatedWork W843989413 @default.
- W2023648202 hasVolume "53" @default.
- W2023648202 isParatext "false" @default.
- W2023648202 isRetracted "false" @default.
- W2023648202 magId "2023648202" @default.
- W2023648202 workType "article" @default.