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The molecular structures were determined by X\u2010ray diffraction studies. The title compounds were applied in halide abstraction studies in order to access cationic species. The reaction of Ph<jats:sub>3<\/jats:sub>PC(Me)Si(Cl)Me<jats:sub>2<\/jats:sub> (<jats:bold>1<\/jats:bold>) with Na[B(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>4<\/jats:sub>] furnished the dimeric phosphonium\u2010like dication [Ph<jats:sub>3<\/jats:sub>PC(Me)SiMe<jats:sub>2<\/jats:sub>]<jats:sub>2<\/jats:sub>[B(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>4<\/jats:sub>]<jats:sub>2<\/jats:sub> (<jats:bold>8<\/jats:bold>). The highly reactive, mesityl\u2010 or <jats:italic>i<\/jats:italic>Pr\u2010substituted cationic species [Ph<jats:sub>3<\/jats:sub>PC(Me)SiMes<jats:sub>2<\/jats:sub>][B(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>4<\/jats:sub>] (<jats:bold>9<\/jats:bold>) and [Ph<jats:sub>3<\/jats:sub>PC(Et)Si<jats:italic>i<\/jats:italic>Pr<jats:sub>2<\/jats:sub>][B(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>4<\/jats:sub>] (<jats:bold>10<\/jats:bold>) could be characterized by NMR spectroscopy. Carrying out the halide abstraction reaction in the sterically demanding ether <jats:italic>i<\/jats:italic>Pr<jats:sub>2<\/jats:sub>O afforded the protonated \u03b1\u2010SiCP [Ph<jats:sub>3<\/jats:sub>PCH(Et)Si(Cl)<jats:italic>i<\/jats:italic>Pr<jats:sub>2<\/jats:sub>][B(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>4<\/jats:sub>] (<jats:bold>6\u2009dec<\/jats:bold>) by sodium\u2010mediated basic ether decomposition, whereas successfully synthesized [Ph<jats:sub>3<\/jats:sub>PC(Et)Si<jats:italic>i<\/jats:italic>Pr<jats:sub>2<\/jats:sub>][B(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>4<\/jats:sub>] (<jats:bold>10<\/jats:bold>) readily cleaves the F\u2212C bond in fluorobenzene. Thus, the ambiphilic character of \u03b1\u2010SiCPs is clearly demonstrated. The less reactive germanium analogue [Ph<jats:sub>3<\/jats:sub>PC(Me)GeMes<jats:sub>2<\/jats:sub>][B{3,5\u2010(CF<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>3<\/jats:sub>}<jats:sub>4<\/jats:sub>] (<jats:bold>14<\/jats:bold>) was obtained by treating <jats:bold>11<\/jats:bold> with Na[B{3,5\u2010(CF<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>3<\/jats:sub>}<jats:sub>4<\/jats:sub>] and fully characterized including by X\u2010ray diffraction analysis. Structural parameters indicate a strong C<jats:sub>Ylide<\/jats:sub>\u2212Ge interaction with high double bond character, and consequently the C\u2212E (E=Si, Ge) bonds in <jats:bold>9<\/jats:bold>, <jats:bold>10<\/jats:bold> and <jats:bold>14<\/jats:bold> were analyzed with NBO and AIM methods.<\/jats:p>","DOI":"10.1002\/chem.202103974","type":"journal-article","created":{"date-parts":[[2021,11,25]],"date-time":"2021-11-25T03:12:53Z","timestamp":1637809973000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["Accessing Cationic \u03b1\u2010Silylated and \u03b1\u2010Germylated Phosphorus Ylides"],"prefix":"10.1002","volume":"28","author":[{"given":"Felix","family":"Kr\u00e4mer","sequence":"first","affiliation":[{"name":"Karlsruhe Institute of Technology (KIT) Institute of Inorganic Chemistry, Division Molecular Chemistry  Engesserstra\u00dfe 15 76131 Karlsruhe Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Michael","family":"Radius","sequence":"additional","affiliation":[{"name":"Karlsruhe Institute of Technology (KIT) Institute of Inorganic Chemistry, Division Molecular Chemistry  Engesserstra\u00dfe 15 76131 Karlsruhe Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7831-1410","authenticated-orcid":false,"given":"Alexander","family":"Hinz","sequence":"additional","affiliation":[{"name":"Karlsruhe Institute of Technology (KIT) Institute of Inorganic Chemistry, Division Molecular Chemistry  Engesserstra\u00dfe 15 76131 Karlsruhe Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Melina E. 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