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Substituent effects (<jats:italic>R<\/jats:italic>\u2009=\u2009alkoxy, alkyl, phenyl, H, <jats:styled-content style=\"fixed-case\">NH<\/jats:styled-content><jats:sub>2<\/jats:sub>, <jats:styled-content style=\"fixed-case\">NMe<\/jats:styled-content><jats:sub>2<\/jats:sub>, halogens) on the stability of these ylides and their neutral counterparts (R<jats:sub>m\u2212<\/jats:sub><jats:styled-content style=\"fixed-case\"><jats:sub>1<\/jats:sub>X<\/jats:styled-content>\u2013<jats:styled-content style=\"fixed-case\">YR<jats:sub>n<\/jats:sub><\/jats:styled-content><jats:sub>\u22121<\/jats:sub>) are analyzed across various X\u2009\u2192\u2009Y bonding scenarios. Fluorine\u2010substituted ylides (e.g., <jats:styled-content style=\"fixed-case\">N<jats:sup>h<\/jats:sup>O<\/jats:styled-content><jats:sub>\/F<\/jats:sub>, <jats:styled-content style=\"fixed-case\">S<jats:sup>h<\/jats:sup>O<\/jats:styled-content><jats:sub>\/F<\/jats:sub>, <jats:styled-content style=\"fixed-case\">S<jats:sup>h<\/jats:sup>S<\/jats:styled-content><jats:sub>\/F<\/jats:sub>, <jats:styled-content style=\"fixed-case\">P<jats:sup>h<\/jats:sup>O<\/jats:styled-content><jats:sub>\/F<\/jats:sub>) and <jats:styled-content style=\"fixed-case\">P<jats:sup>h<\/jats:sup>O<\/jats:styled-content><jats:sub>\/<jats:styled-content style=\"fixed-case\">OMe<\/jats:styled-content><\/jats:sub> exhibited the highest stability compared to their neutral forms. Bond length and Wiberg bond order analyses reveal significant double bond character of the X\u2013Y bond, confirming the hypervalent structure of the molecule. Molecular electrostatic potential (<jats:styled-content style=\"fixed-case\">MESP<\/jats:styled-content>) analysis shows reduced charge separation and delocalized electron density of the molecule, supporting a hypervalent ylene resonance form (<jats:styled-content style=\"fixed-case\">R<jats:sub>m<\/jats:sub>X<\/jats:styled-content>\u2009=\u2009<jats:styled-content style=\"fixed-case\">YR<jats:sub>n<\/jats:sub><\/jats:styled-content><jats:sub>\u22122<\/jats:sub>). These findings provide insights into the stability and electronic structure of hypervalent molecules, aiding the design of novel compounds.<\/jats:p>","DOI":"10.1002\/jcc.70122","type":"journal-article","created":{"date-parts":[[2025,5,14]],"date-time":"2025-05-14T09:58:54Z","timestamp":1747216734000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Unveiling the Hypervalent Electronic Structure of Main Group Zwitterions: Ylides or Ylenes? 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